A matching \( M \) in a graph \( G \) is a set of pairwise non-adjacent edges. \( M \) is maximal if it is not contained in any other matching of \( G \). A minimum maximal matching is a maximal matching of minimum size, and its cardinality is the saturation number of \( G \). Maximal matchings serve as an effective model for characterizing certain real-world problems, while the saturation number captures information about their worst-case scenarios in a certain sense. In this paper, we prove that the saturation number of any phenylene chain with \( n \) benzenoids is \( 2n \). We also derive a formula to enumerate minimum maximal matchings via the transfer matrix method. Furthermore, we determine the extremal phenylene chains with \( n \) benzenoids achieving the largest and smallest number of minimum maximal matchings, respectively.