The purpose of this study was to determine whether the Big Five personality factors, measured by the NEO Personality Inventory Five-Factor Inventory (Costa & McCrae, 1992), and vocational confidence across Holland's hexagon, measured by the Skills Confidence Inventory (SCI; Betz, Borgen, & Harmon, 2005), were useful in discriminating among educational majors and career aspirations for 312 Taiwanese university students. The Big Five and confidence, in combination, significantly differentiated among 4 college majors and 7 career aspirations in a Taiwanese university sample. Big Five Agreeableness and SCI Realistic, Investigative, and Conventional confidence emerged as most salient in the discrimination. Differences by sex, major, and career aspiration were mostly consistent with social cognitive career theory, Holland's theory, and prior U.S. research.