Opportunistic maintenance stands out as an effective strategy for minimizing maintenance costs and enhancing system efficiency. Despite its importance, current opportunistic maintenance models are often tailored to specific system types, particularly those with series structures, or they offer heuristic approaches for multi-component redundant systems. This paper shifts focus to the most common of such systems, the parallel–series system. We approach the optimization of opportunistic maintenance in a parallel–series system through a Markov Decision Process framework, utilizing phase-type approximations of individual component hazard functions. Addressing the challenge of the curse of dimensionality in the action space, this study conducts a thorough structural analysis of the optimal opportunistic maintenance policy, deriving a pruning procedure, which can reduce the extensive combinatorial action space into a more manageable linear complexity without sacrificing the strategy’s effectiveness in parallel–series systems. Building on this more manageable action space, we introduce a more efficient algorithm leveraging the proposed pruning procedure for determining the optimal opportunistic maintenance policy. The effectiveness and practical applicability of this approach are rigorously demonstrated through comprehensive numerical experiments.