A simple and convenient method based on sessile drop technique for measuring surface tensions of polymer and nematic liquid crystal (LC) is described. Contact angles formed by drops of probe liquids and a nematic LC on a photocurable polymer were measured. The surface energies were evaluated using the Fowkes method, Neumann's equation, and new equations developed based on Neumann's approach. The values of surface tensions were used to evaluate the interfacial interaction in term of work of adhesion between the LC and polymer. Further, the effect of dichroic dye on the extent of interaction and work of adhesion was examined by measuring contact angle in consequence of dye addition. A difference in work of adhesion between the lower and higher dye-doped LC droplets gave an indication of affinity relationship between polymer and LC molecules. A change in work of adhesion resulted in variability of nematic director configurations inside phase separated LC droplets embedded in polymer matrix; when viewed under polarizing optical microscope. Thus, our approach of estimating surface energy of polymer and LC has found to be useful in determining interaction at polymer–LC interface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41137.