Here, we present a simulation study of temperature‐dependent electronic transitions in BiVO3 (BVO) and BiNbO3 (BNO) using density functional theory (DFT) together with generalized gradient approximation (GGA) and two‐dimensional correlation analysis (2D‐CA). The results indicate that heat accumulation can accelerate the degeneracy of V‐3d orbital in BVO and the splitting of Nb‐4d orbital in BNO at 750 K. We found changes in the type of d–p hybrid orbital as follows, for BVO: V‐dx2+y2 + dZ2‐O‐2pz → V‐dx2+y2‐O‐2pz; and for BNO: Nb‐dx2+y2‐O‐2pz → Nb‐dx2+y2 + dZ2‐O‐2pz. Furthermore, we found changes in the type of hybrid orbital leading to the following electron–electron interactions, for BVO: t2g (V‐dZ2‐O‐2pz) + eg (V‐dx2+y2‐O‐2pz) → t2g (V‐dx2+y2‐O‐2pz); and for BNO: t2g + eg (Nb‐dx2+y2 + dZ2‐O‐2pz) → t2g (Nb‐dx2+y2‐O‐2pz) + eg (Nb‐dz2‐O‐2pz). The electronic transitions are determined by a charge‐transfer from the occupied O‐2p4 orbitals to the unoccupied V‐3d3 (or Nb‐4d3) and Bi‐6p3 orbitals. Due to the temperature‐dependent electronic structure closely related to these electronic transitions, this study provides a new perspective for the design and improvement of BFO‐based temperature‐sensitive devices.