Direct photocatalytic coupling of methanol to ethylene glycol (EG) is highly attractive. The first metal oxide photocatalyst, a tantalum-based semiconductor, is reported for preferential activation of C-H bonds within methanol to form hydroxymethyl radical (* CH2OH) and subsequent C-C coupling to EG. The nitrogen doped tantalum oxide (N-Ta2O5) photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.