The direct methane to methanol (DMTM) conversion is often referred to as a 'dream reaction' with enormous potential to alter energy sector and chemical industry. After O-2-activation, Cu-exchanged zeolites form CuxOy species that activate CH4 and release it in the form of CH3OH upon interaction with H2O. Despite extensive research efforts in the last years, several questions concerning the influence of materials composition and process parameters on the reaction mechanism remain open. Herein, we characterize Cu-MOR zeolites with different composition by operando X-ray absorption spectroscopy (XAS), monitoring their spectroscopic response under two characteristic DMTM reaction protocols varied in the duration of the key reaction steps. Linear Combination Fit (LCF) analysis of the time-resolved X-ray absorption near edge structure (XANES) spectra collected during CH4-loading and steam-assisted CH3OH extraction enabled to quantify the abundance of different Cu species during these two steps. Data analysis revealed a positive linear correlation between the methanol yield generated per incorporated copper and the Cu(I) component formed during the CH4-loading step. Cu(I) development during CH4-loading is accompanied by modifications in the extended X-ray absorption fine structure (EXAFS) spectra suggesting substantial rearrangement in the active site structure. The obtained results provide new mechanistic insights for the DMTM over Cu-MOR.