By using the semiempirical time-dependent Hartree-Fock PM3 calculations we have studied the frequency-dependent second- and third-order polarizabilities of thiophene-, pyrrole-nitro polyene systems. The PM3 predicted limiting average second-order polarizabilities increase in the order : pyrrole-> furan-> thiophene-nitro polyene systems. The average and longitudinal third-order polarizabilties have the following order : pyrrole->thiophene->furan-nitro polyene systems. In these trends. we suggest that pyrrole group is the best donor group among the three polyene systems.