Display omitted Thiol functionalization of two-dimensional (2D) metal sulfides has been demonstrated as an effective approach to enhance the sensing performances. However, most thiol functionalization is realized by multiple-step approaches in liquid medium and depends on the dispersity of 2D materials. Here, we utilize a three-dimensional (3D) In2S3 nano-porous structure that self-assembled from 2D components as the nanoreactor, in which the surface-absorbed thiol molecules from the chemical residues of the nanoreactor are used for the in-situ covalent functionalization. Such functionalization is realized by facile heat the nanoreactor at 100 °C, leading to the recombing sulfur vacancies with thiol-terminated groups. The NO2 sensing performances of such functionalized nanoreactor are investigated at room temperature, in which In2S3-100 exhibits a response magnitude of 21.5 towards 10 ppm NO2 with full reversibility, high selectivity, and excellent repeatability. Such high-performance gas sensors can be attributed to the additional electrons that transferring from the functional group into the host, thus significantly modifying the electronic band structure. This work provides a guideline for the facile in-situ functionalization of metal sulfides and an efficient strategy for the high performances gas sensors without external stimulus.