Cellulose nanofibrils (CNFs) have been studied extensively over the past decade. Their applications, e.g., as fillers for nanocomposites, stabilizers for Pickering emulsions, and scaffolds for cell culture, are mostly dictated by interfacial adhesion. In general, the individual surface free energy values of the constituents of a material correlate with its adsorption and desorption behaviors.In the present study, we estimated the surface free energy values of thin films composed of CNFs using traditional contact angle methods based on the Wenzel equation and van Oss−Chaudhury− Good theory. The accuracy and utility of the estimated surface free energy values were verified by close matching between the obtained adhesion energy values and the actual interfacial adsorption behaviors of the CNFs. Therefore, the evaluated surface energy values are expected to be a feasible tool for designing of interfacial interactions between CNF surfaces and other materials.