The optical absorption, ionic conductivity, electronic conductivity, and gas separation properties have been evaluated for flexible composite films of ionically conductive polymers that contain partially embedded arrays of ordered, crystalline, p-type Si microwires. The cation exchange ionomer Nafion, and a recently developed anion exchange ionomer, poly(arylene ether sulfone) that contains quaternary ammonium groups (QAPSF), produced composite microwire array/ionomer membrane films that were suitable for operation in acidic or alkaline media, respectively. The ionic conductivity of the Si wire array/Nafion composite films in 2.0 M H2SO4(aq) was 71 mS cm−1, and the conductivity of the Si wire array/QAPSF composite films in 2.0 M KOH(aq) was 6.4 mS cm−1. Both values were comparable to the conductivities observed for films of these ionomers that did not contain embedded Si wire arrays. Two Si wire array/Nafion membranes were electrically connected in series, using a conducting polymer, to produce a trilayer, multifunctional membrane that exhibited an ionic conductivity in 2.0 M H2SO4(aq) of 57 mS cm−1 and an ohmic electrical contact, with an areal resistance of ∼0.30 Ω cm2, between the two physically separate embedded Si wire arrays. All of the wire array/ionomer composite membranes showed low rates of hydrogen crossover. Optical measurements indicated very low absorption (<3%) in the ion-exchange polymers but high light absorption (up to 80%) by the wire arrays even at normal incidence, attesting to the suitability of such multifunctional membranes for application in solar fuels production.