High resolution solid state C-13 nuclear magnetic resonance (SS NMR) measurements were carried out on poly(p-xylylene) (PPX). The samples comprised vapor-deposited specimens as well as pure alpha and beta polymorphs of this polymer. The measurements were performed using cross-polarization and magic angle spinning (CP/MAS) techniques. Density functional theory gauge-including-atomic-orbital (DFT GIAO) calculations of NMR shielding parameters C-13 sigma(ii) were performed for the optimized geometry and structure of a xylylene trimer, acquired from the X-ray data, including intermolecular interactions. Two-dimensional phase adjusted spinning sideband (21) PASS) correlation was employed for the assignment of the values of the principal elements C-13 delta(ii) of the chemical shift tensor (CST). A comparative analysis of shielding (sigma(ii)) versus chemical shift (delta(ii)) parameters showed substantial differences between the molecular dynamics of alpha and beta polymorphs. This observation was further supported by the measurements of C-13 T-1 relaxation times and the analysis of cross-polarization kinetics. Frequency switched Lee-Goldburg heteronuclear correlation (FSLG HETCOR) for the H-1-C-13 system was used in order to analyze molecular packing in both polymorphs. As a result of all of the above measurements, new insight into the mechanism of thermal phase transition from the alpha to the beta polymorph of poly (p-xylylene) is presented.