Abstract: Antimony (Sb) is a critical raw material for the global development of high-tech industries, and its ores are strategically important resources under strict national control. Research on analytical techniques for Sb metal ores is crucial to improve resource utilization and support a new round of strategic action for mineral prospecting breakthroughs. Owing to the complex composition of metal ores, complete decomposition remains challenging, and Sb readily undergoes hydrolysis during analytical procedures. In this paper, pretreatment and determination methods for Sb are systematically reviewed. The key challenges in pretreatment include achieving complete sample decomposition, improving digestion efficiency, and minimizing sample loss. Although acid digestion plays a pivotal role in ore pretreatment, issues such as incomplete decomposition, hydrolysis, and volatilization persist. Complete decomposition of refractory ores can be achieved by alkali fusion; however, the resulting high salt content must be carefully considered. Powder pellet pressing and fusion are commonly used pretreatment methods for X-ray fluorescence spectrometry (XRF), although they are limited by preparation precision and crucible corrosion. Atomic absorption spectrometry (AAS) and hydride generation–atomic fluorescence spectrometry (HG-AFS) provide excellent selectivity and sensitivity, enabling accurate determination of Sb over concentration ranges of 10⁻⁶–50% and 10⁻⁶–10⁻³, respectively. However, these techniques allow limited multi-element analysis and require strict control of matrix interferences. XRF is environmentally friendly and enables simultaneous multi-element determination, but it relies heavily on matrix-matched reference materials for calibration. The use of synthetic reference materials has expanded its linear range, allowing determination of Sb in the range of 0.5%–83.5%; however, limitations in detection limits and sensitivity remain. Spectrophotometry and polarography exhibit relatively low analytical efficiency and are generally unsuitable for batch sample analysis. Volumetric methods offer good reliability and stability and are applicable for determining Sb at concentrations above 0.5%. However, they require strict operational control, are time-consuming, and are susceptible to interference from coexisting ions. Inductively coupled plasma-mass spectrometry (ICP-MS) provides high sensitivity and low detection limits, enabling the determination of Sb at the 10⁻⁹ level. Nevertheless, it suffers from a narrow linear range and significant spectral interferences. In contrast, inductively coupled plasma-optical emission spectrometry (ICP-OES) offers a wide linear range and can determine Sb concentrations from 10⁻⁶ to 20%. It demonstrates distinct advantages in the analysis of Sb in metal ores and represents a promising direction for the development of analytical techniques in this field. For metal ores, they are difficult to be decomposed completely and faced with the hydrolysis. In this paper, the pretreatment and determination methods are systematically summarized. The key challenges of pretreatment include ensuring complete decomposition, improving digestion efficiency, and minimizing sample loss. Although acid digestion plays a pivotal role in the pretreatment of ores, challenges of incomplete decomposition, hydrolysis, and volatilization have remained unsolved. Although the complete decomposition of refractory ores could be achieved by alkali fusion, the resulting high salt contents have to be taken into account. Powder pellet and fusion are the pretreatment methods for XRF, while these are limited by preparation precision and crucible corrosion. AAS and HG-AFS are characterized by high selectivity and sensitivity, allowing the precise determination of Sb concentrations ranging from 10⁻⁶ to 50 % and from 10⁻⁶ to 10⁻³, respectively. However, few elements can be detected simultaneously and the matrix interference need to be controlled. XRF is environmentally friendly and enables simultaneous multi-element determination. Nevertheless, the calibration curves depend on the matched reference materials. While synthetic reference materials have extended its concentration ranges of standard curves from 0.5% to 83.5%, detection limit and sensitivity are relatively poor. Spectrophotometry and polarography exhibit relatively low analytical efficiency and are generally not recommended for batch sample analysis. Volumetric methods are well-established and reliable, and are suitable for the determination of Sb at concentrations above 0.5%. Nevertheless, they entail stringent operational requirements, are time-consuming, and suffer from interferences caused by coexisting ions. ICP-MS offers high sensitivity and a low detection limit, enabling the determination of Sb down to the 10⁻⁹ level. In contrast, ICP-OES features a wide linear range, enabling the determination of Sb over the range from 10⁻⁶ to 20%. It exhibits distinct advantages for the determination of Sb in metal ores and represents a development direction for analytical techniques targeting Sb in metal ores.