AbstractFor 2D MXenes (Mo2C and Ti3C2), the fundamental hot‐carrier‐related processes are studied by using the first‐principles calculation, including the material electronic structures, indirect/direct transitions for hot‐carrier generation, electron–electron and electron–phonon scatterings during hot‐carrier transport, and electronic modulation on material to evaluate the potentials of 2D MXenes in hot‐carrier photodetection. It is found that Mo2C and Ti3C2 show higher hot‐carrier generation efficiencies than Au in energy over 1 eV, especially for Mo2C, which shows better transport performance than Ti3C2. Biaxial strain to adjust the electronic structure of Mo2C is further used to optimize the hot‐carrier transport properties. A Mo2C/MoGeSiN4 hot‐electron photodetector is proposed, which shows that the compressive strain (−4%) on Mo2C material enables a twofold enhancement of the quantum efficiency and responsivity. The Monte Carlo device simulation predicts an extremely high responsivity up ≈176 mA W−1 at the communication wavelength of 1550 nm, which is one order of magnitude over the existing hot‐carrier devices and can be competitive with the existing semiconductor‐based photodetectors.