Poly(ionic liquid)s are an innovative class of materials with promising properties in gas separation processes that can be used to boost the neat polymer performances. Nevertheless, some of their properties such as stability and mechanical strength have to be improved to render them suitable as materials for industrial applications. This work explored, on the one hand, the possibility to improve gas transport and separation properties of the block copolymer Pebax® 1657 by blending it with poly[3-ethyl-1-vinyl-imidazolium] diethyl phosphate (PEVI-DEP). On the other hand, Pebax® 1657 served as a support for the PIL and provided mechanical resistance to the samples. Pebax® 1657/PEVI-DEP composite membranes containing 20, 40, and 60 wt.% of PEVI-DEP were cast from solutions of the right proportion of the two polymers in a water/ethanol mixture. The PEVI-DEP content affected both the morphology of the dense membranes and gas transport through the membranes. These changes were revealed by scanning electron microscopy (SEM), time-lag, and gravimetric sorption measurements. Pebax® 1657 and PEVI-DEP showed similar affinity towards CO2, and its uptake or solubility was not influenced by the amount of PIL in the membrane. Therefore, the addition of the PIL did not lead to improvements in the separation of CO2 from other gases. Importantly, PEVI-DEP (40 wt.%) incorporation affected and improved permeability and selectivity by more than 50% especially for the separation of light gases, e.g., H2/CH4 and H2/CO2, but higher PEVI-DEP concentrations lead to a decline in the transport properties.