Herein, we report our findings on the novel ability of aluminum chloride (AlCl3) in fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol [HFIP] to selectively deprotect the N-benzyloxycarbonyl group (N-Cbz). The salient features of this method are good functional group tolerance including other reducible groups, cost-effectiveness, easy-to-handle, safe protocol, amenable to scale-up, high yields, and ambient temperature reactions. The methodology would serve as an excellent alternative to the use of pyrophoric hydrogen gas and metal catalyst reagents that pose severe safety and environmental concerns. The most notable feature of this methodology is the orthogonal deprotection of the N-Cbz group in the presence of O- and N-Bn protecting groups, hence, expanding the scope for designing synthetic routes to target compounds requiring multiple functional group transformations.