Red emitters based on CaAl12O19:Mn4+ have been attracting extensive attention due to their advantages of being rare-earth-free and chemically stable. However, their relatively low luminescence efficiencies will seriously hinder their application in light-emitting diodes (LEDs). In this regard, the promising red phosphors of CaAl12O19:Mn4+ were synthesized with enhanced luminous efficiency by introducing the coexisting phase of MgAl2O4. Importantly, an approximately 5 times enhancement of integrated intensity in the emission spectrum was observed for the phosphor with the coexisting phase compared to that with a single phase. Their crystal structures, morphologies and photoluminescence properties and the mechanism of improved luminescence were systematically investigated. Upon exciting them by using near-ultraviolet or blue LEDs, an efficient red emission was achieved with a maximum peak at ∼658 nm. In order to evaluate their potential application, a warm white LED and a plant growth LED were fabricated by using the prepared phosphors in combination with YAG:Ce3+ and InGaN-based blue chips.