Methane, abundant but inert, contributes significantly to greenhouse gases, primarily through combustion, which emits vast amounts of CO2. Photocatalytic methane coupling at ambient temperature offers a method to convert it into ethane, a more versatile hydrocarbon. This study examines selective methane-to-ethane coupling using heterogeneous photocatalysts comprising silver and palladium salts dispersed on titania. Through a combination of ex-situ and in-situ techniques along with DFT simulations, distinct mechanisms and active phases in these catalysts are revealed. In silver catalysts, dispersed cationic Ag+ species are crucial for methane activation, while in palladium catalysts, palladium primarily exists in metallic form during coupling. Water strongly enhances coupling rates with both catalysts. DFT modeling identified methane adsorption sites, suggesting methane activation via •OH radicals, experimentally supported by EPR under in-situ conditions.