Charge-transfer complexes formed between pregabalin as electron donor with different electron acceptors, picric acid (HPA), chloranilic acid (H2CA) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have been studied in the liquid and solid states. The stoichiometries of complexes were found to be 1:1 molar ratio between donor and acceptors for the systems PRG-HPA and PRG-H2CA while a ratio of 1:2 was detected for the PRG-DDQ interaction at the characteristics CT absorption bands of the formed complexes. Characterizations of the formed CT-complexes were based on elemental analyses, photometric titration measurements, IR, 1H NMR spectra along with the thermogravimetric analysis of the CT-complexes. The characteristic physical constants (KCT), (m), (DG), (ID), (f), (ECT) of the formed CT-complexes are shown to be strongly dependent on the type and structure of the electron acceptors.