Direct conversion of methane (CH4) to fuels and other high value-added chemicals is an attractive technology in the chemical industry; however, practical challenges to sustainable processes remain. Herein, we report the preparation of a heterostructured Co-doped MgO-based catalyst through topological transformation of a MgCo-layered double hydroxide (LDH) calcination from 200 to 1100 °C. Remarkably, the catalyst can activate CH4 coupling to produce C2H6 with a selectivity of 41.60 % within 3 h under full-spectrum irradiation through calcination of LDH at 800 °C. Characterization studies and catalytic results suggest that the highly dispersed active sites and large interfaces amongst the Co-doped MgO-based catalysts enable surface activation of CH4 to methyl (CH3*), in turn promoting coupling of CH3* to C2H6. This study introduces a promising pathway for photodriven CH4 coupling to give high value-added chemicals by using layered double hydroxides as a precursor.