This work deals with the photophysics of novel pyridinium betaine based on 2-pyridin-1-yl-1 H -benzimidazole (SBPa) substituted symmetrically by mono- (Th 2 SBPa) and bi-thiophene fragments (Th 4 SBPa). The study is based on a combination of steady-state, femtosecond transient absorption spectroscopic measurements supported by PCM-(TD)DFT calculations. It is found that the two step ICT process (S 0 → S 2 excitation followed by S 2 (CT) → S 1 (CT) internal conversion) occurring for the parent molecule remains unaffected for Th 2 SBPa while the situation is less clear for Th 4 SBPa. Actually, for both molecules, a new decay route involving the π-electron system localized in thiophenic groups is responsible for the production of triplet states. Involvement of this new route in the parallel production of S 1 (CT) is strongly suspected.