In this article, we delve into the optimal scheduling challenge for many-to-many on-orbit services, taking into account variations in target accessibility. The scenario assumes that each servicing satellite is equipped with singular or multiple service capabilities, tasked with providing on-orbit services to multiple targets, each characterised by distinct service requirements. The mission’s primary objective is to determine the optimal service sequence, orbital transfer duration and on-orbit service time for each servicing satellite, with the ultimate goal of minimising the overall cost. We frame the optimal scheduling dilemma as a time-related colored travelling salesman problem (TRCTSP) and propose an enhanced firefly algorithm (EFA) to address it. Finally, experimental results across various scenarios validate the effectiveness and superiority of the proposed algorithm. The principal contribution of this work lies in the modeling and resolution of the many-to-many on-orbit service challenge, considering accessibility variations — a domain that has, until now, remained unexplored.