AbstractKinetic studies on the formation of charge transfer complexes of 2‐(1H)‐pyridinethione with π‐acceptors p‐chloranil and p‐bromanil in dipolar aprotic solvent N,N‐dimethylformamide have been carried out spectrophotometrically at various temperatures. The reaction follows an overall third order rate equation, through first order with respect to π‐acceptors and second order with respect to the 2‐(1H)‐pyridinethione. The rates were found to increase with increasing temperature. Activation parameters, ΔH≠ and ΔS≠ have been calculated for the charge transfer complexes. The structure of the products was confirmed by their elemental analysis, IR,1H NMR and mass spectrometry. Conductometric method has been used to investigate the electron donor‐acceptor complex formation. The stoichiometries of these complexes have been established and their conductance (σP−) and molar conducti