The blend surfaces of poly[oxy(n-decylsulfonylmethyl)ethylene] (CH3-10SE) and poly (3-hexylthiophene) (P3HT) with different weight ratios were prepared by spin coating the polymer solution mixtures. In this study, their surface properties such as surface morphology, chemical composition, molecular structure, and wettability were systematically studied and correlated with liquid crystal (LC) alignment behaviors on the blend films. Therefore, we found that CH3-10SE part with a well-ordered side chain structure predominantly affects the both of wettability and LC alignment behavior of the blend films while there was no clear association between the wettability and the LC alignment behavior. (C) 2011 Elsevier Inc. All rights reserved.