A novel multi‐color emitting Na2YMg2V3O12:Sm3+ phosphor was synthesized using a solid‐state reaction, and its crystal structure, luminescence properties, and thermal stability were studied. Charge transfer within the (VO4)3− groups in the Na2YMg2V3O12 host led to a broad emission band between 400 and 700 nm, with a maximum at 530 nm. The Na2Y1−xMg2V3O12:xSm3+ phosphors exhibited a multi‐color emission band under 365 nm near‐ultraviolet (near‐UV) light, consisting of the green emission of the (VO4)3− groups and sharp emission peaks at 570 nm (yellow), 618 nm (orange), 657 nm (red), and 714 nm (deep red) of Sm3+ ions. The optimal doping concentration of Sm3+ ions was found to be 0.05 mol%, and the dipole–dipole (d–d) interaction was primarily responsible for the concentration quenching phenomenon. Using the acquired Na2YMg2V3O12:Sm3+ phosphors, commercial BaMgAl10O17:Eu2+ blue phosphor, and a near‐UV light‐emitting diode (LED) chip, a white‐LED lamp was designed and packaged. It produced bright neutral white light, manifesting a CIE coordinate of (0.314, 0.373), a color rendering index (CRI) of 84.9, and a correlated color temperature (CCT) of 6377 K. These findings indicate the potential of Na2YMg2V3O12:Sm3+ phosphor to be used as a multi‐color component for solid‐state illumination.