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In the presented manuscript an influence of the mesoporosity generation in commercial ZSM-5 zeolite on its catalytic performance in two environmental processes, such as NO reduction with ammonia (NH3-SCR, Selective Catalytic Reduction of NO with NH3) and NH3 oxidation (NH3-SCO, Selective Catalytic Oxidation of NH3) was examined. Micro-mesoporous catalysts with the properties of ZSM-5 zeolite were obtained by desilication with NaOH and NaOH/TPAOH (tetrapropylammonium hydroxide) mixture with different ratios (TPA+/OH-= 0.2, 0.4, 0.6, 0.8 and ∞) and for different durations (1, 2, 4 and 6 h). The results of the catalytic studies (over the Cu-exchanged samples) showed higher activity of this novel mesostructured group of zeolitic materials. Enhanced catalytic performance was related to the generated mesoporosity (improved Hierarchy Factor (HF) of the samples), that was observed especially with the use of Pore Directing Agent (PDA) additive, TPAOH. Applied desilication conditions did not influence significantly the crystallinity of the samples (X-ray diffraction analysis (XRD)), despite the treatment for 6 h in NaOH solution, which was found to be too severe to preserve the zeolitic properties of the samples. The modified porous structure and accessibility of acid sites (increased surface acidity determined by temperature programmed desorption of ammonia (NH3-TPD)) influenced the red-ox properties of copper species introduced by ion-exchange method (temperature programmed reduction with hydrogen (H2-TPR). Increased acidity of the micro-mesoporous samples, as well as the content of easily reducible copper species resulted in a significant improvement of Cu-ZSM-5 catalytic efficiency in the NH3-SCR and NH3-SCO processes.