Polycyclic aromatic hydrocarbons are of special interest due to their promising nonlinear optical and magnetic properties. A series of acene-linked zethrenes and bisphenalenyls comprising from five to nine benzene rings in the linker group have been computationally studied by the DFT UB3LYP/6-311++G­(d,p) quantum-chemical modeling of their electronic structure, possible spin states, and exchange interactions. The zethrenes with octacene and nonacene linkers as well as bisphenalenyls comprising heptacene, octacene, and nonacene linker groups have been revealed to possess tetraradicaloid nature, which makes them promising building blocks for organic optoelectronic and spintronic devices. The results obtained open a way of constructing tetraradicaloid organic molecules characterized by the presence of two types of paramagnetic centers.