This research developed the Occupational Values Inventory (OVI), a 30-item measure that expands the content coverage of work values by linking into a broad range of O*NET occupational descriptors, including Work Activities and Work Contexts, along with salary data from the Bureau of Labor Statistics. The OVI assesses 11 work values—Interpersonal, Outdoor, Physical, Leadership, Salary, Prestige, Variety, Interest, Work Hours, Knowledge Utilization, and Autonomy—providing an updated and refined coverage of work values relevant to people and occupations in the modern labor market. Study 1 (N = 768) developed and refined the OVI’s scales using conceptual and psychometric criteria, also reporting initial evidence in support of reliability and validity. Studies 2 and 3 further evaluated the reliability and criterion-related validity of the OVI based on longitudinal samples of recent graduates from universities (N = 816) and community colleges (N = 560). OVI scales and profiles were correlated with occupational aspirations and choice; work value fit with O*NET occupations correlated with subjective career outcomes including career choice satisfaction. The OVI can provide objective assessment of work values fit between people and a wide range of occupations, and may be used in a range of vocational research and applied settings.