Starch-based materials seem to be an excellent alternative for conventional plastics used in various applications. Microfibralted cellulose can be used to improve the surface properties of starch-based materials. This study aims to analyze the surface properties of starch-microfibrillated cellulose materials. The surface properties of films were evaluated by ATR-FTIR, surface roughness, water wettability, and surface free energy. The surface homogeneity between corn starch and microfibrillated cellulose (MFC) fibers was confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Microscopic analyses of the film surfaces confirm good compatibility of starch and MFC. The addition of MFC increased the surface roughness and polarity of developed starch/MFC materials. The surface roughness parameter has increased from 1.44 ± 0.59 to 2.32 ± 1.13 for pure starch-based materials and starch/MFC material with the highest MFC content. The WCA contact angle has decreased from 70.3 ± 2.4 to 39.1 ± 1.0°, while the surface free energy is 46.2 ± 3.4 to 66.2 ± 1.5 mJ·m−2, respectively. The findings of this study present that surface structure starch/MFC films exhibit homogeneity, which would be helpful in the application of MFC/starch materials for biodegradable packaging purposes.