A series of sodium poly(styrene sulfonate)-block-poly(4-tert-butylstyrene) (NaPSS-b-PtBS) copolymers and related homopolymers were characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The homopolymers included polystyrene (PS), poly(4-tert-butylstyrene) (PtBS), sodium poly(4-styrene sulfonate) (NaP4SS), sodium poly(styrene sulfonate) (NaPSS) with various sulfonation levels, and partially sulfonated PtBS (PtBSS). The structures of NaPSS and PtBSS were elucidated, and the effect of sulfonation level on the NaPSS FT-IR spectrum was studied. The characteristic peaks for NaPSS and PtBSS in FT-IR and NMR spectra were identified.