Poly(p-methylstyrene) (Pp-MS) was synthesized at three different temperatures of 50, 150 and 250 °C via bulk thermal polymerization method. The assignment of all stereosequences at triad and pentad levels for two quaternary aromatic carbons and hexad level for methylene carbon was carried out by 13C liquid nuclear magnetic resonance spectroscopy (NMR) in deuterated chloroform at similar conditions. The probability of meso addition (Pm) was calculated from second quaternary aromatic carbon and used to predict the relative intensities of methylene and first quaternary aromatic carbon by Bernoullian and first-order Markov statistical models. The results were compared with experimental data. It is shown that the Bernoullian statistics fit better than first-order Markov model for all three samples. The results indicate that Pm increases by increasing polymerization temperature. The corresponding Pm values determined for synthesized Pp-MSs at 50, 150 and 250 °C were 0.383, 0.392 and 0.404, respectively. It was observed that higher resolutions and better splitting patterns were achievable by increasing the NMR acquisition temperature from 20 to 50 °C. When temperature increased during NMR acquisition, the resolution improved for the first and second quaternary aromatic carbons and methylene carbon, though there was no splitting pattern observed for methyl carbon atom at the para-position of the aromatic ring.