The modification of inert boron nitride by carbon doping to make it an efficient photocatalyst has been considered as a promising strategy. Herein, a highly efficient porous BCN (p-BCN) photocatalyst was synthesized via precursor reconfiguration based on the recrystallization of a new homogeneous solution containing melamine diborate and glucose. Two crystal types of the p-BCN were obtained by regulating the recrystallization conditions of the homogeneous solution, which showed high photocatalytic activities and a completely different CO2 reduction selectivity. The CO generation rate and selectivity of the p-BCN-1 were 63.1 μmol·g−1·h−1 and 54.33%; the corresponding values of the p-BCN-2 were 42.6 μmol·g−1·h−1 and 80.86%. The photocatalytic activity of the p-BCN was significantly higher than those of equivalent materials or other noble metals-loaded nanohybrids reported in the literature. It was found that the differences in the interaction sites between the hydroxyl groups in the boric acid and the homolateral hydroxyl groups in the glucose were directly correlated with the structures and properties of the p-BCN photocatalyst. We expect that the developed approach is general and could be extended to incorporate various other raw materials containing hydroxyl groups into the melamine diborate solution and could modulate precursors to obtain porous BN-based materials with excellent performance.