Dynamic contact angle (DCA) and adhesion tension relaxation (ATR) for poly(vinyl alkylate)s (PVAls) were measured. Advancing contact angle initially increased with an increase in the side-chain-length and after a maximum at C10, it decreased, while receding contact angle showed a complex behaviour. A large contact-angle hysteresis was observed. DCA also depended on the dipping velocity. Results on ATRs showed that the surface molecule of these PVAls had large molecular mobility. Reproducibility of ATR was also observed. These phenomena were explained by the reorientation of the segment at polymer/water or polymer/air interface so as to minimize interfacial free energy.