The multiferroic perovskite oxide BiFeO3 (BFO), other than the conventional semiconductor oxides, is a promising absorber for water photolysis in photoelectrochemical cells (PECs). However, BFO has very limited ability to split the water because of its inefficient light absorption in the visible region, large carrier recombination rate, reduced surface area and poor charge transport. A way to overcome these limitations is the incorporation of a narrow direct band gap semiconductor such as La2NiMnO6 (LNMO), and to create a plum pudding type composite with BFO. The BFO/LNMO composite with a band gap of 1.34–1.48 eV (depending on the molar fraction of LNMO) has an enhanced photocurrent (~14.07 mA/cm2) and an applied bias photon-to-current conversion efficiency (~9.61%). The improved PEC performance is attributed to its improved light absorbance in the visible region, better carrier transport, increased surface area and higher dielectric constant. In respect of narrow direct band gap, BFO/LNMO composite is also quite promising for photovoltaic application.