Five and six member ring azaheterocyclic derivatives are reported as highly valuable scaffolds in modern medicinal chemistry and pharmacy (drugs, as antibacterial, antifungal, anti-inflammatory, antihypertensive, anticoagulants, diuretics, anticancer, antidepressant, etc.), organic materials for opto-electronics (fluorescent and electroluminescent materials, semiconductor devices, sensors and biosensors) and agriculture (mainly herbicides and grow up factors), etc. As a result, obtaining of such derivatives continues to arouse a strong interest from academia and industry. During the last decades, microwave (MW) and ultrasound (US) assisted reactions has become a successful tool applied in modern organic and medicinal chemistry. In comparison with conventional thermal heating (TH), both microwave and ultrasound irradiation have several important advantages: spectacular accelerations of chemical reactions, increased selectivity, shorter reaction times, higher yields and higher product purities. The MW and US assisted reactions become in many cases ecologically friendly, having milder reaction conditions, suppressing side reactions, energy saving, using small amounts, or no organic solvents, lower costs and simplicity in handling and processing. Also, in some cases described in the literature, reactions that did not occur under classical TH were only successful if carried out under MW and/or US irradiation. As part of our ongoing research in the field of azaheterocyclic derivatives, we present herein the main results obtained in the last few years by our group in the field of synthesis and developing of new environmentally friendly methods for preparation of these derivatives using MW and US technologies. The main reaction pathway studied was acylation, alkylation, quaternization, esterification, etherification, halogenation, 3+n cycloadditions reactions, etc. Certain advantages of microwave (MW) and ultrasound (US) assisted reactions was observed: better selectivity, higher yields, decreasing of the amount of used solvent comparative with TH, decreasing of the reaction time from hours to minutes, decreasing of the consumed energy, milder reaction conditions; consequently these reactions could be considered environmentally friendly. The anticancer, antibacterial, antifungal and antituberculosis activity of some azaheterocycles derivatives was determined, some of the compounds having an excellent biological activity. Some of the obtained compounds are promising leading drug candidates. Acknowledgements Authors are thankful to Romanian Ministry of Research, Innovation and Digitization, Program 1-Development of the national R & D system, Subprogram 1.2—Institutional performance—RDI excellence financing projects, Grant no. 554 PFE-CDI and CNCS-UEFISCDI, project number PN-III-P4-IDPCE- 2020-0371, for financial support. The authors are also thankful to the project POC/448/1/1 Research Center with Integrated Techniques for Atmospheric Aerosol Investigation in Romania-RECENT AIR (grant agreement MySMIS no. 127324) for infrastructure used and the POSCCE-O 2.2.1, SMIS-CSNR 13984-901, No. 257/28.09.2010 Project, CERNESIM, for NMR experiments.