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• C-CuO-Cu 2 O/CF hybrid was synthesized by a facile candle flame annealing. • The composition was confirmed by XRD, Raman and TEM techniques. • The C-CuO-Cu 2 O/CF electrode showed excellent photoelectrochemical activity. • High photoelectrochemical performance was due to carbon coating and hybrid composition. In this work, carbon coated-CuO-Cu 2 O composite on copper foam (C-CuO-Cu 2 O/CF) is synthesized by candle flame treatment and is evaluated as a photocathode of photoelectrochemical water splitting (PEC). The photocurrent density of C-CuO-Cu 2 O/CF electrode can reach −1.2 mA cm−2 (at 0 V vs. RHE), which is about 12 times higher than that of Cu 2 O/CF. The high PEC performance is due to the carbon modification and the unique composition which increase the carrier concentration and reduce the carrier recombination rate and promote charge transfer at electrode-electrolyte interface. Our results proves that candle flame annealing is a promising way for the rational design of carbon modified photoelectrodes. [ABSTRACT FROM AUTHOR]