This study sought to understand how receptivity to working abroad initially develops. Australian graduating business students were surveyed prior to entry to full‐time work and 2 years later after entry, providing a sample of 213 full‐time employees (average age 23 years). Taking a social cognitive career theory approach, beyond individual and organizational control variables, when new young male or female employees had high outcome expectancies (personal agency), had little family influence and no partner (few barriers), and worked in organizations with an international focus (opportunities), their receptivity to international careers increased compared with when they were students. Appraisals of self‐capabilities (personal agency) appeared relevant dependent on destination. When employees preferred country ease for work, and when as students they had low self‐efficacy for international work, their willingness to relocate to work in developing, but not developed, countries was reduced. Suggesting some factors may not be as relevant for later, as for initial, development of receptivity, outcome expectancies and organizational international focus were not related to increased receptivity in 104 older graduate employees (average age 36 years). The influence of home barriers, organizational focus and self‐capabilities on the development of receptivity to international careers and to working in developing countries was discussed, taking into account age, gender and marital status.