Two‐photon excited fluorescence materials with sufficient responsiveness to magnetic field are essential for applications such as 3D mapping of magnetic field distributions based on magneto‐optical effect. In this study, a two‐photon excited magneto‐photoluminescence (MPL) in the intermolecular exciplex of 1,1‐bis[(di‐4‐tolylamino)phenyl]cyclohexane and tris(2,4,6‐trimethyl‐3‐(pyridin‐3‐yl)phenyl)borane (TAPC:3TPYMB) is observed. This MPL can be attributed to the promotion of delocalization of excitons in the exciplex under two‐photon excitation, resulting in a weakened spin‐exchange interaction and thereby enhancing the magnetic field‐sensitive spin conversion process. The temperature‐dependent MPL further validates the strong correlation between the delocalization of excitons in the exciplex and the enhanced MPL observed during temperature variation. Combining the penetration capability and magneto‐optical effect of two‐photon excited fluorescence in TAPC:3TPYMB exciplex, a novel magnetic sensor suitable for 3D mapping of magnetic field distributions is further developed. The present work not only enhances the understanding of the magneto‐optical coupling mechanism but also opens up opportunities for the application of molecular materials in opto‐spintronic devices.