摘要： TiS2 has been intensively studied as an electrode material and a thermoelectric material for energy storage and conversion applications due to its high electrical conductivity. Understanding the influence of defects on electrical transport is of importance not only to resolve the long-standing question concerning the nature of TiS2, but also for the rational design of TiS2 based devices for energy scavenging applications. In this study, we integrate photoemission spectroscopy, Raman spectroscopy, and electrical transport measurements to determine the chemical compositions dominated by defects and their influence on the doping and electrical properties. Our results demonstrate that TiS2 is a heavily self-doped semiconductor with the Fermi level close to the conduction band, which serves as the conclusive experimental evidence regarding the semiconducting nature of TiS2. The doping effect is sensitive to the (subtle) changes in the chemical composition. The electron donation from the Ti interstitials (Tii) to the TiS2 host explains the high carrier concentration. The Ti Frenkel pair (TiF) acting as the acceptor is responsible for the decrease in the electron carrier concentration and electrical conductivity. High conductivity maintains upon partial oxidization, indicating the oxidization-tolerance in terms of the electronic structure. Our results provide valuable insight into the evolution of electronic properties modulated by defects that reveal unambiguously the self-doped semiconducting nature of TiS2 and chemical- and environment-tolerance of TiS2 as an advanced energy scavenging material.