The completion of vocational education and training (VET) and the subsequent school-to-work transition are important steps on the career pathway. The school-to-work transition is a long-term process with unclear boundaries involving a number of potentially difficult aspects. Psychological resources for successful school-to-work transitions are reflected in the multidimensional psychosocial construct of career adaptability. The goal of the present study was to examine the role of selected demographic and school-related variables in predicting career adaptability and four components of career adaptability (concern, control, curiosity, and confidence) among VET graduates. Participants in this study were 3,028 Czech students approximately 1–2 months before graduation from vocational education and training, aged from 18 to 26 years (M = 18.97, SD = 1.09). The 24-item Career Adapt-Abilities Scale was used to measure career adaptability. Results from multiple linear regression analyses found that five out of ten predictor variables positively predicted the career adaptability or career adaptability components. These variables were the gained paid work experience in the field of study, one-off or multiple use of career guidance services, male gender, tertiary education of the father, and the field of study completed with a school-leaving examination. The variables that did not statistically predict career adaptability were family structure, maternal education, grades (GPA), repetition of a grade, and change of the field of study. Implications for career guidance are discussed.