C-13 longitudinal relaxation times and nuclear Overhauser enhancements were measured as a function of temperature in three magnetic fields for a series of poly(1-naphthylalkyl acrylate)s in 1,1,2,2-tetrachloroethane-d2. Variable-temperature C-13 transverse relaxation time measurements at 75.4 and 125.7 MHz also were undertaken. The relaxation data have been described by using various models for main-chain segmental motion and side-chain internal rotations. Among these, the Dejean-Laupretre-Monnerie (DLM) model offered the best description of segmental motion for the poly(1-naphthylalkyl acrylate) chains. Internal rotations about the side-chain bonds, including naphthyl internal motion, were described by hindered rotations superimposed on segmental motions, the latter being described by the DLM model. An attempt was made to correlate rates and activation energies associated with the various modes of reorientation in the aforementioned polymers with the rates of excimer formation between the side-chain naphthalene chromophores.