Lithium‐containing silicates have been considered as a considerable alternative for luminescent materials. In this study, a novel cyan‐emitting phosphor, Na3LiHf2Si3O12: Eu2+, was successfully synthesized via cationic substitution with Na4Hf2Si3O12: Eu2+ as the initial model. The crystal structure, morphology, and luminescence performance of Na4‐xLixHf2Si3O12: Eu2+ were investigated in detail. The substitution of Li+ for Na+ site causes a significant blue‐shift of the emission band in the range of 550–500 nm and a smaller full width at half maximum. As a result, a cyan phosphor Na3LiHf2Si3O12: Eu2+ that can be effectively excited by near‐ultraviolet and high‐energy beams is obtained. The mechanism of emission regulation was proposed based on the transformation of crystal structure and luminescence performance. In addition, the thermal quenching and cathodoluminescence behaviors were also studied. The results show that cation substitution is an effective method to design new lithium‐containing silicate phosphors.
