The graduate labour market is highly competitive but little is known about why students vary in their development of employability. This study contributes to the literature by applying goal-setting theory and the job demands–resources model to investigate how motivational processes influence students’ proactive career behaviours. We tested four hypotheses using structural equation modelling and moderation/mediation analysis using a nested model approach; 432 undergraduates from 21 UK universities participated in this cross-sectional study. The results showed that students higher in mastery approach had greater perceived employability mediated by two proactive career behaviours (skill development and network building). Students’ career goal commitment was associated with all four proactive career behaviours (career planning, skill development, career consultation and network building). Students’ academic and employment workloads did not negatively impact their proactive career behaviours. University tutors and career services should therefore encourage students to set challenging career goals that reflect mastery approach.