Tetravalent manganese is known as one of the candidate luminous centers to obtain red emission. There are still unclear factors in Mn4+-activated oxide phosphors to achieve intense emission. In this paper, we studied the photoluminescence properties of double perovskite-type tantalates AE2LaTaO6 (AE = Ca, Sr, and Ba) activated with Mn4+. All AE2LaTaO6:Mn exhibited Mn4+-emission in the deep red region under excitation by near-ultraviolet-green light (300–570 nm) at room temperature. Co-substitution of Mg2+, Al3+, and Ti4+ compensates unbalanced charge caused by oxygen defects, resulting in the enhancement of Mn4+-emission. The present cosubstitution effect is different from the usual cosubstitution, such as the replacement of two Al3+ by Mn4+ and Mg2+, taking into consideration the charge balance between cations. Theoretical calculation of band structures based on density functional theory suggests the presence of two kinds of quenching schemes in AE2LaTaO6:Mn, photoionization and electron transfer from va...