Tellurium (Te)-doped black silicon (Si) with enhanced absorption and photoelectric performance over a broad wavelength range of 0.2−2.5 μm was obtained using femtosecond (fs) laser irradiation in liquid water. Prior to laser irradiation, the Si sample was covered with a Te thin film (thickness 200 nm) over an adhesion layer of Cr (thickness 5 nm). Surface analyses by scanning electron microscopy and three-dimensional confocal microscopy evidence the presence of hierarchical surface structures combining quasi-periodic stripes with a spatial period of about 5 μm and subwavelength laser-induced periodic surface structures directed in directions parallel and perpendicular to the direction of the laser polarization, respectively. Moreover, the incorporation of Te generates intermediate levels within the Si bandgap. The Te-doped black Si shows a significant enhancement of the absorption, which reaches values of about 48% in the UV and visible (0.2−1.1 μm) and 70% in the near-infrared (1.1−2.5 μm) spectral ranges, respectively, due to the synergistic effects of multiscale surface structures and Te incorporation. Moreover, the surface reflectance is reduced to almost zero across the entire spectrum. The Te-doped black Si sample is used to realize a photodetector which displays an impressive photoelectric capability, being characterized by a responsivity of 328 mA/W, and an external quantum efficiency of 49.27% at a voltage bias of −10 V for 1064 nm light illumination, with rising and falling times of 55 and 67 ms, respectively. These figures remarkably outperform the response of unprocessed Si under the same experimental conditions.