In this work, based on first-principles calculations, we propose that electrene can be considered as an electron-donating substrate to drive the phase transition of MoTe2 from the H to T′ phase, which is a topic of long-standing interest and importance. In particular, new electrenes Ca2XN2 (X = Zr, Hf) are predicted with the existence of a nearly free two-dimensional (2D) electron gas and ultralow work functions. In MoTe2/Ca2XN2 donor–acceptor heterostructures, we find significantly large charge transfer (∼0.4e per MoTe2 unit cell) from Ca2XN2 to MoTe2, which stabilizes the T′ phase and decreases the phase transition barrier (from ∼0.9 to ∼0.5 eV per unit cell). In addition, the phase transition of MoTe2 on Ca2XN2 remains effective as the interlayer distance varies. It therefore can be confirmed conclusively that our results open a new avenue for phase transition study and provide new insights for the large-scale synthesis of metastable high-quality T′-phase MoTe2.