Two-dimensional heterostructures with excellent properties are potential for high performance optoelectronic applications, since the ultimate thickness limit is possible to be broken with the advent of atomically thin materials. Yet the studies have also been largely constrained by the low physical doping space and absorption rates due to the atomic-thickness layers, and the efforts for high carrier concentrations and gain remain a significant challenge. Herein, high concentration of Er3+ ions are in-situ doped in WS2 and WSe2 atomic layers by chemical vapor deposition (CVD) method. The prepared layers are characterized by atomic force microscopy, transmission electron microscopy, photoluminescence (PL) spectroscopy, and Raman spectroscopy, respectively. 13–14 at% of Er3+ doping concentration in WSe2 and WS2 are examined by energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) with high consistency. A microregion fixed-point transfer technique is used to transfer the WS2(Er3+) monolayers onto the WSe2(Er3+) monolayers to form vertical van der Waals heterojunctions. Excellent performances are measured from the WS2(Er3+)/WSe2(Er3+) photodetector with the photoresponsivity of up to 67.4 A/W, external quantum efficiency of 13,202 %, and detectivity of 7.07 × 1011 Jones. Our results prove the effectiveness of Er3+ in-situ doping in WS2(Er3+)/WSe2(Er3+) heterojunctions for high-performance photodetectors.