Poly(xylylenes) are an important class of thermoplastics that are readily prepared by thermolysis of [2.2]paracyclophane or xylene precursors to afford xylylene monomers that condense and polymerize on solid surfaces to give polymer films. As most poly(xylylenes) are insoluble due to a high degree of crystallinity, characterization by solid-state nuclear magnetic resonance spectroscopic techniques is necessary. In this paper we describe the preparation of poly(xylylene) (P1), poly(2-ethylxylylene) (P2), poly(2-chloroxylylene) (P3), poly(2,3-dichloroxylylene) (P4), and poly(alpha,alpha,alpha’,alpha’-tetrafluoroxylylene) (P5) and their characterization using solid-state C-13 cross polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy.