A simple solution process was employed to decorate WO3 nanoparticles on 2D conductive Ti3C2TX MXene sheets to arrange the MXene/WO3 hybrid structure. The prepared hybrid composites were established by the Raman scattering, X‐ray diffraction, and microscopy studies evidently. The designed hybrid structure, for the first time, was engaged with PEDOT:PSS to alter the hole transport layer (HTL) of perovskite hybrid module for the highly efficient planar solar cell and X‐ray detector. The derived outcomes revealed a high power conversion efficiency of 12.26 ± 0.12% for the constructed perovskite solar cell with MXene/WO3/PEDOT:PSS HTL. Similarly, the fabricated X‐ray photodetector with MXene/WO3 blended HTL device attained a superior sensitivity of 3.67 ± 0.03 mA Gy−1·cm−2. The results envisaged that HTL/perovskite interface was effectively tuned by the MXene/WO3 heterostructure through their active interface for transfer/collection of charges and appropriately altered energy band alignment, which gave the nod for easy to charge extraction and shortest charge carrier lifetime.