Quinoidal bithiophene has recently been introduced (Varnavski, O. et al. J. Phys. Chem. Lett. 2015, 6, 1375-1384) as a very promising isolated organic compound for intramolecular singlet fission (iSF) with an outstanding SF quantum yield of ≈180%. In contrast, another recent study (Ren, L. et al. J. Am. Chem. Soc. 2015, 137, 11294-11302) revealed that quinoidal tetrathiophenes have no activity in the iSF process and are strong fluorophores instead, with measured fluorescent quantum yields up to 53.1%. Using DFT and TD-DFT methods, the authors of the second contribution attributed the marked differences between these compounds to faster reverse T2 → S1 intersystem crossing processes in the tetrathiophenes. To address this unprecedented discrepancy, quinoidal bithiophene and tetrathiophene compounds and their derivatives are carefully examined using the CASPT2 technique. Theoretical evidence is provided through detailed investigation of CASPT2 potential energy surfaces of different singlet and triplet states involved in the iSF process. Through comparison of the CASPT2 results with the CASSCF and RAS-2SF data, it is found that the dynamic electron correlation present in the CASPT2 method plays a crucial role for correct description of the multiexciton nature of the triplet pair 1[TT] state in quinoidal bi- and tetrathiophenes. Effects of substitution and structural modification on iSF activity of these compounds are also examined using the CASPT2 method where the obtained results are in accordance with previous experimental predictions. These results contribute to a better understanding of the iSF mechanism in quinoidal systems which could be relevant for designing new iSF active compounds.