To simplify the complicated synthetic techniques so that getting CuII-SSZ-13 zeolites with ideal structures and CuII cations distribution, and to interrogate CuII cations dynamics dependent NH3 mediated performance of selective catalytic reduction (NH3-SCR) of NO and hydrothermal stability, a microwave-assisted hydrothermal synthesis route was performed to prepare CuII exchanged SSZ-13 zeolite catalysts. The effects of synthetic temperature and time on the structure of SSZ-13 zeolite and NH3-SCR performance are clarified. The types and numbers of CuII species of fresh and hydrothermal aged samples were precisely explored. The NH3-SCR activity, N2 selectivity of fresh and aged CuII-SSZ-13 zeolites synthesized by different conditions are evaluated, respectively. Experimental characterizations demonstrate that the CuII-SSZ-13 zeolites can be synthesized with short crystallization time assisted with microwave treatment. The microwave synthesis temperature and time can affect the nucleation and growth process of SSZ-13 and thus resulting in SSZ-13 with different framework structures and various affinity to CuII ions. When the temperature and time are 175 degrees C and 9 h, the as-synthesized CuII-SSZ-13 sample shows a stable framework structure, large specific surface area, and more [Z2CuII] speciation. This sample also shows excellent catalytic activity and hydrothermal stability. Characterization results also show that the microwave treatment can strengthen the Al-O-Si bonds in the zeolite framework. Our work provides a facile strategy to synthesize CuII-SSZ-13 zeolite and atomic-level understanding of catalytic property and hydrothermal stability.