The cyclic hexamer of phenylene sulfide (CHPS) is studied as a precursor of poly(p-phenylene sulfide) (PPS). The CHPS is one of the soluble components obtained by the extraction of poly(p-phenylene sulfide) with tetrahydrofuran (THF). Differential thermal analysis (DTA) is used to verify the purified cyclic compound. Fourier transform-infrared spectroscopy (F-IR) and Raman spectroscopy are also employed. The spectra of the CHPS are compared with those of PPS and interpreted based on the symmetry of the molecules. Specifically, the C-H out-of-plane bending modes (840-800 cm(-1)) are indicative of the crystal structure and are utilized to identify two crystalline forms, alpha and beta, of the CHPS. The spectrum of the polymer obtained from the CHPS is also reported.