Spontaneous polarization and inversion symmetry breaking in ferroelectric materials lead to their use as photovoltaic devices. However, further advancement of their applications are hindered by the paucity of ways of reducing bandgaps and enhancing photocurrent. By unravelling the correlation between ferroelectric materials' responses to solar irradiation and their local structure and electric polarization landscapes, here we show from first principles that substantial bulk photovoltaic effect enhancement can be achieved by nanolayering PbTiO3 with nickel ions and oxygen vacancies ((PbNiO2)x(PbTiO3)(1-x)). The enhancement of the total photocurrent for different spacings between the Ni-containing layers can be as high as 43 times due to a smaller bandgap and photocurrent direction alignment for all absorption energies. This is due to the electrostatic effect that arises from nanolayering. This opens up the possibility for control of the bulk photovoltaic effect in ferroelectric materials by nanoscale engineering of their structure and composition.