KYF4 polycrystalline materials singly doped with Sm3+ ions and co-doped with Tb3+/Sm3+ ions were synthesized by the hydrothermal technique. The optical spectra of all samples were measured at room temperature. The features of the ligand field and the optical properties of Sm3+ ions in KYF4 were studied via Judd-Ofelt theory. A three-level model was used to estimate the validity of the Judd-Ofelt analysis for KYF4:Sm3+. The luminescence quenching of KYF4:Sm3+ relates to energy transfer through cross relaxation between Sm3+ ions. For KYF4:Tb3+,Sm3+, the luminescence of Sm3+ ions is enhanced due to the energy transfer process from Tb3+ to Sm3+. The chromaticity features of the luminescence from KYF4:Tb3+,Sm3+ were estimated by the chromaticity coordinates and correlated color temperature (CCT). The dominant interaction mechanism and the energy transfer parameters for the Sm3+-Sm3+ and Tb3+-Sm3+ energy transfer processes were analyzed by using the Inokuti-Hirayama model.