The equilibrium geometries of LiOCP, NaOCP, LiSCP, and NaSCP were calculated at the MP2 and QCISD/6311G* levels of theory. It was found that all four have pi-type cyclic conformers. In case of the former two, this form is the most stable isomer, whereas in LiSCP and NaSCP, no other conformations but the cyclic exist. Vibrational frequencies and ionization energies were calculated to facilitate vapor phase identification. Semiempirical quantum chemical and molecular mechanics simulations were also undertaken to study their behavior in solutions; they are expected to dissociate, and the resulting pseudohalide anions are linear. Thus the existence of the pi-complex cannot be demonstrated in solution.