We are reporting the optical study of two types of poly (3-thienylene vinylene) (PTV) derivatives with linear and bulk side chain configurations. The first one, poly(3-dodecylthienylenevinylene) with controlled regioregularity (PTV-CR) with an alkyl side group, showed a high degree of crystallinity, whereas the second one, imide-PTV with an electron deficient imide side group, is amorphous. Continuous wave-photoinduced absorption revealed different features of the long-lived triplet absorptions, with the geminately generated triplet–triplet pair in imide-PTV bearing more intrachain characteristics with fast recombination kinetics (<10 μs). On the other hand, the isolated triplet in PTV-CR generated by intersystem crossing had more interchain characteristics with slow recombination kinetics (ms). The decay of the triplet–triplet pair in imide-PTV is monomolecular even at a high pump intensity of 240 mW/cm2, whereas the isolated triplets in PTV-CR recombine bimolecularly at a very low pump intensity of 10 mW/cm2. Grazing incidence X-ray diffraction, doping induced absorption, and various dependences of the photoinduced absorption spectrum have corroborated the finding that reduced interchain interaction favors the formation of a correlated triplet–triplet pair, a precursor to two independent triplets formed via fission.