Density functional theory (DFT) calculations have been employed to study the adsorption and dehydrogenation mechanism of CHX (x = 1-4) on the non-doped Cu(1 1 1) and M-Cu(1 1 1) surfaces (M = Pd, Pt, Rh and Ni). The adsorption intensity of CH2, CH and C species were higher on M-Cu(1 1 1) surface than non-doped Cu(1 1 1) surface. The minimum energy paths for CH4 sequential dehydrogenation were also studied, suggesting that CH4 desorption was more favorable than the dissociation due to the weakly physical adsorption. Interestingly, it was found that CHx dissociation was promoted in different degree on the M-Cu(1 1 1) surface both kinetically and thermodynamically, with the trend of Rh > Ni > Pt > Pd.