In this study, we successfully synthesised a series of La7O6(BO3)(PO4)2 (LBPO): Sm phosphors. We conducted microstructural analysis of the doped samples using X-ray diffraction, comparing them with the host material. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were utilised to analyse the intermolecular chemical bonds and surface chemical states of the optimal LBPO:0.07 Sm3+ sample, respectively. Upon exposure to 404 nm near-ultraviolet irradiation, visible light emissions from Sm3+ transitions from 4G5/2 to 6H5/2, 6H7/2, and 6H9/2 were observed. The best doping concentration of Sm3+ is 0.07 mol, with content quenching attributed to energy transfer interactions. The optical band gap was determined theoretically and experimentally. Additionally, we measured the decay lifetime and photoluminescence properties, indicating the potential of the optimal LBPO:0.07 Sm3+ phosphor as a red component in solid-state lighting.