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Despite narrowing math achievement gaps, gender disparities in STEM career aspirations persist among top-performing students worldwide. Drawing on Situated Expectancy-Value Theory (SEVT), this study analyzes PISA 2022 data from 81 countries to examine why high-achieving females remain less likely than males to pursue STEM careers. Multilevel structural equation modeling reveals that females report lower math confidence and intrinsic value, and higher perceived cost—factors that significantly reduce their STEM aspirations. Moreover, institutional gender inequality moderates these effects through three mechanisms: reinforcement (e.g., family discrimination), compensation (e.g., resource scarcity), and channeling (e.g., limited civil liberties). These findings highlight the critical interaction between psychological and structural barriers, offering new directions for policy aimed at fostering gender equity in STEM talent development globally.