The surface morphologies and properties of polystyrene (PS)/poly(2-vinylpyridine) (PVP) blend films cast on the mica substrate from ethylbenzene solution were investigated upon controlling different weight ratios and solvent evaporation rates. A near-honeycomblike surface morphology of the PS/PVP blend film formed under controlling the solvent evaporation rate due to the effect of Marangoni-Benard convection. The results of static water contact angles, X-ray photoelectron spectroscopy, solvent selective etching, and treatment by water illustrated that the near-honeycomblike structures on the surface of PS/PVP blend films were different for different weight ratios of PS and PVP. After treatment with water for several minutes, PVP islands-like structure emerged in the holes of the film for a PS/PVP weight ratio of 4/1, and a quasihexagonal arrangement of alternate big and small PVP droplets emerged on the top layer of the film for a PS/PVP weight ratio of 7/1. The formation mechanisms of different surface structures and their response behaviors to water were discussed.