Reverse intersystem crossing (RISC) from triplet to singlet states has been recently introduced to photophysics of organic chromophores. One type of RISC occurs in donor (D)–acceptor (A) composites that form an exciplex manifold in which the energy difference, ΔEST between the lowest singlet (S1) and triplet (T1) levels of the exciplex is small (<100 meV) thus allowing RISC at room temperature. This adds a delayed component to the photoluminescence emission that is widely known as thermally activated delayed fluorescence. Here, it is found that the electroluminescence in organic light‐emitting diodes (OLED) based on electron D–A exciplex is significantly enhanced (up to ≈40%) by applying magnetic field, due to the existence of an additional spin‐mixing channel between singlet and triplet states in the exciplex. The large magneto‐electroluminescence (MEL) in N,N,N′,N′‐tetrakis(4‐methoxyphenyl)benzidine: tris‐[3‐(3‐pyridyl)mesityl]borane [D–A] based OLEDs is demonstrated. These results are supported by magneto‐photoluminescence (MPL) measurements, and density functional theory calculations. Importantly, it is found that both MEL and MPL are thermally activated indicating the dominant role of the RISC process. The MEL(B) response using the Δg mechanism is analyzed, where the electron and hole g‐values are different from each other because they reside in different molecules.