The electronic structure of organic sigma-type polyradical including 2,4,6-tridehydropyridine radical cation (246-TDHP) and three isomers of tetradehydrobenzene (TDHB) have been studied using a computationally robust and cost-effective second-order multireference perturbative model which provides a balanced treatment of nondynamic and dynamic contributions to the electron correlation problem in the ground or excited electronic states which are imperative for predicting structural properties (e.g., ground state multiplicity, energy gaps between high-spin and low-spin states, etc.) of polyradicals. Energy gaps are useful to capture insight into the degree of interaction between the radical sites. An important finding of this study is that the tetraradicals considered here possess singlet ground states, contrary to Hund's rule. Present findings are in close agreement with the available high-level ab initio estimates at attainable cost implying that a perturbative description of the systems is adequate. The impact of N+ on the nature of ground state for the 246-TDHP have also analyzed. The singlet-triplet energy gaps for 1245- and 1234-TDHB are smaller than for o-benzyne mainly due to the ring strain. 1235-TDHB is 14.42 and 11.05 kcal/mol lower in energy than 1245- and 1234-isomers, respectively. IVO-SSMRPT predicts (1)A(1)-B-3(2) and (1)A(1)-B-5(2) gaps of 25.84 and 105.15 kcal/mol, respectively for the 246-TDHP cation.