Laser-induced graphene (LIG) has aroused a wide range of research interests ranging from micro-nano energy devices to the Internet of Things (IoT). Nevertheless, the non-degradability of most-used synthetic polymer carbon sources poses a serious threat to the environment. In this work, ecofriendly chitosan-based derivatives, including carboxymethyl chitosan (CMCS), chitosan oligosaccharide, and chitosan hydrochloride, are successfully converted into LIGs for the first time via a convenient one-step CO₂ laser engraving at ambient air. The obtained LIGs are characterized by a three-dimensional hierarchical porous structure and exhibit good sheet conductivity. The consecutive carbonization and graphitization mechanism of target precursors induced by laser heat accumulation is also deeply discussed. Besides, based on a mechanically reliable LIG/CMCS composite film and tribo-negative acrylic/polyimide anti-layers, two contact-separation mode triboelectric nanogenerators are built and their power densities range from 1.44 to 2.48 mW cm^-2. These devices with long cycle life can be used for low-frequency mechanical energy harvesting and commercial capacitance charging, which could be potentially applied in the wireless sensor network nodes. Such a family of chitosan derivatives paves a new route for LIG synthesis and provides new ideas for ecofriendly LIG electronics.