The preparation of porous films (average size variation from 1 to 32 μm) of a 1:1 blend of chitosan with poly(EG-ran-PG) by the controlled evaporation of water from a 2 wt % aqueous acetic acid solution is reported. Interestingly, the blend exhibited porosity that could be tailored from 1 to 32 μm with the temperature of preparation of the blend film. The powder X-ray diffraction, Fourier transform infrared, and differential scanning calorimetry analyses of the films suggested the formation of partially miscible blends. Temperature-induced phase separation of the blend appears to be the mechanism of pore formation. The tensile strength, cytotoxicity, and biocompatibility of the blend films for the growth of mesenchymal stem cells were assessed vis-a-vis chitosan. The 1:1 blend film was observed to lack cytotoxicity and was also viable for the growth of mesenchymal stem cells. The tensile properties of the 1:1 blend were superior to those of the chitosan film. The simple preparation of porous, nontoxic, and biocompatible films could find use as a scaffold in the growth of tissue, and especially bone tissue, in wound dressing, and in filtration if a better control over pore size is achieved.