EPR is an unique spectroscopic method for getting information about the principal properties of polymers with particular electronic properties. By this way also the possibilities of the recently developed high-field ESR in the 2 mm-waveband is illustrated. The high field ESR was applied for the study of the dynamics of polarons in conjugated polymers. The rate of the quasi-one-dimensional (1D) intrachain polaron motion and of the three-dimensional (3D) interchain electron hopping has been estimated separately. Both processes depends as well on the molecular structure as on preparation conditions and as a result on the arrangements of molecule segments in the polymer solids. The presence of the absorbed oxygen from ambient atmosphere lead to the existence of positively charged polarons with spin S = 1/2. This report presents results of the investigation of polaron dynamics in an initial and treated P(3-OT) samples at 2-mm waveband EPR. The data obtained on the study of anisotropic dynamics of charge carrier can be used in the understanding and interpretation of electronic processes in molecular poly(3-alkylthiophene)-based solar cells and in polymer transistors.