The complicated interplay between microstructure and tribo‐corrosion behavior has long been an intriguing problem in the field of advanced materials engineering. This study systematically investigated the effects of different laser energy densities (LED) on the surface morphology, microstructure, and tribo‐corrosion behavior of Ti‐6Al‐4V produced using laser powder bed fusion (LPBF) technology. The surface morphology and microstructure of the specimens were characterized in detail using various characterization techniques such as optical microscopy (OM), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). Additionally, a self‐assembled friction‐corrosion equipment was employed to evaluate the tribo‐corrosion behavior of the samples at different LED settings. The results showed that the LED had a significant effect on the surface morphology, microstructure, and tribo‐corrosion behavior of the Ti‐6Al‐4V. Increasing the LED lead to reduced surface roughness, weakened keyhole and segregation phenomena, more distinct β grain boundaries, and coarser acicular α phase. Moreover, the tribo‐corrosion behavior initially improved and then declined with increasing LED. Furthermore, tribo‐corrosion product and mechanism of the Ti‐6Al‐4V alloy prepared by LPBF were revealed. This study is of great significance for understanding the relationship between the microstructure and tribo‐corrosion behavior of Ti‐6Al‐4V manufactured by LPBF.This article is protected by copyright. All rights reserved.