Metal doping between black phosphorus (BP) layers has great advantages in modulating electronic properties. Here, the effects of Cu intercalation on charge transfer and carrier dynamics are investigated by theoretical calculations. Relative to the pristine bilayer BP, Cu suppresses the nonradiative electron-hole recombination, reducing the major pathways of energy and current loss. Furthermore, we investigate a novel pn homogeneous junction based on the Cu-doped bilayer BP, which shows enhanced transport properties and Ohmic contact characteristics. This is because doping leads to the transformation of BP from p-type to n-type, charge accumulation on conduction bands allows electrons to be easily transferred to the p-type bilayer BP, and associated electrical properties can be modulated by the doping concentration. This study has fundamental importance for understanding structure-property relationships in metal intercalation, which is an important guidance for integration and interlayer engineering for two-dimensional materials.