Nowadays, many researchers are interested in the development of chemistry of azacrown ethers, especially with the derivatives which contain both perhydrotriazine moiety and crown ether cycle. In some previous publications the authors have firstly communicated about the elaboration of novel method which allowed us to prepare dibenzo(perhydrotriazino)aza-14-crown-4 ether derivatives by condensation reaction of polyether (I) with thiourea or guanidine in the presence of ammonium acetate at room temperature. The yields of these compounds prepared in acetic acid were about 73 percent. However, the time of this reaction was rather long (about 13 h) what brings certain limits to possible practical applications of the target compounds. Therefore, for optimizing the synthetic method, in this report, the authors have successfully fulfilled this reaction by using irradiation energy without acetic acid. All the analytical results, physicochemical constants and spectroscopic data showed that all the substances obtained from both used methods are identical same. The biological activities of the prepared (perhydrotriazino)aza-14-crown-4 ether derivatives have been tested.