Health professionals dual practice has received increasing attention, particularly in the context of the universal health coverage movement. This paper explores the determinants of doctors' choices to become a dual practitioner and of dual practitioners' choices to allocate time to the private sector in the capital cities of Mozambique, Guinea Bissau and Cape Verde. The data are drawn from a survey conducted in 2012 among 329 physicians. We use a two-part model to analyse the decision of both public and private practitioners to become dual practitioners, and to allocate time between public and private sectors. We impute potential earnings in public and private practice by using nearest-neighbour propensity score matching. Our results show that hourly wage in the private sector, number of dependents, length of time as a physician, work outside city, and being a specialist with or without technology all have a positive association with the probability of being a dual physician, while number of dependents displays a negative sign. Level of salaries in the public sector are not associated with dual practice engagement, with important implications for attempts aimed at retaining professionals in the public sector through wage increases. As predicted by theory that recognises doctors' role in price setting, earnings rates are not significant predictors of private sector time allocation; personal characteristics of physicians appear more important, such as age, number of dependents, specialist without technology, specialist with technology, and three reasons for not working more hours in the private sector. Answers to questions about the factors that limit working hours in the private sector have significant predictive power, suggesting that type of employment in the private sector may be an underlying determinant of both dual practice engagement and time allocation decisions.