Optically active defects often play a crucial role in governing the light emission as well as the electronic properties of materials. Moreover, defect-mediated states in the midgap region can trap electrons, thus opening a path for the recombination of electrons and holes in lower energy states that may require phonons in the process. Considering this, we have probed electron–phonon interaction in halide perovskite systems with the introduction of defects and investigated the thermal effect on this interaction. Here, we report Raman spectroscopic study of the thermal evolution of electron–phonon coupling, which is tunable with the crystal growth conditions, in the halide perovskite systems Cs2AgInCl6 and Cs2NaInCl6. The signature of electron–phonon coupling is observed as a Fano anomaly in the lowest frequency phonon mode (51 cm−1), which evolves with temperature. In addition, we observe a broad band in the photoluminescence (PL) measurements for the defect-mediated systems, which is otherwise absent in defect-free halide perovskite. The simultaneous observation of the Fano anomaly in the Raman spectrum and the emergence of the PL band suggests the defect-mediated midgap states and the consequent existence of electron–phonon coupling in the double perovskite.