Abstract A high Schottky barrier height (Φ B ) is one of the essential prerequisites for achieving high‐performance self‐powered Schottky‐barrier diode (SBD)‐based photodetector. The Φ B value is predominantly determined by the metal function and interface quality of the metal/semiconductor contact. 2D MXenes with adjustable work functions and dangling bond‐free properties are promising building blocks for constructing self‐powered SBD with high Φ B . Herein, a novel Ti 3 C 2 T x MXene/Si hexagonal microhole array (SiHMA) van der Waals SBD is developed for the first time via a feasible solution process. Significantly, the device possesses a large Φ B up to ≈1.07 eV, which is among the highest for the Si‐based SBD. In consequence, the Ti 3 C 2 T x /SiHMA SBD yields a large responsivity up to 302 mA W −1 and detectivity as high as 5.4 × 10 13 Jones in a self‐powered model, surpassing the performance of most 2D material/Si photodiodes reported to date. Furthermore, it is demonstrated that featured and reliable fingertip photoplethysmogram (PPG) signals can be detected using the self‐powered SBD, enabling us to further accurately extract the heart rate (HR), and blood pressures (BP) using the PPG‐only method. This work paves the way for the construction of high‐performance MXenes‐based self‐powered SBDs for health monitoring.