Hexacyclic systems have extensive applications in chemistry, combinatorics, and materials science, especially in the characterization of molecular structures and network topologies. The maximal matching polynomial is a fundamental graph invariant that encodes crucial structural and combinatorial information of graphs, which plays a key role in studying the matching properties and structural stability of graphs. In this study, we derive a general computational formula for the maximal matching polynomial of hexacyclic systems, which can be efficiently applied to any hexacyclic structure composed of hexagonal rings. Consequently, a computational formula for the number of maximal matchings of an arbitrary hexacyclic system can be derived. Furthermore, we prove that among all hexacyclic systems with the same length, the linear hexacyclic system has the minimum saturation number.