The 13C-NMR spectra of radical and anionic polystyrene have been studied. Resolution of the aromatic C1 spectra has been made by computer. The resolced peaks have been assigned as pentad sequences and their probablities have been calculated. Experimental and cal-culated resultes show that the sequence distributions of radical and anionic polystyrene obey first order Markovian statistics. The polymers observed are all syndiotactic-rich.