This paper investigates the selective maintenance of systems that perform multi-mission in succession. Selective maintenance is performed on systems with limited break time to improve the success of the next mission. In general, the duration of the mission is stochastic. However, existing studies rarely take into account system availability and the repairpersons with different skill levels. To solve this problem, a new multi-mission selective maintenance and repairpersons assignment model with stochastic duration of the mission are developed. To maximize the minimum phase-mission reliability while meeting the minimum system availability, the model is transformed into an optimization problem subject to limited maintenance resources. The optimization is then realized using an analytical method based on a self-programming function and a Monte Carlo simulation method, respectively. Finally, the validity of the model and solution method approaches are verified by numerical arithmetic examples. Comparative and sensitivity analyses are made to provide proven recommendations for decision-makers.