In this study, a new source of insect chitin was proposed. Insect chitin was extracted from cicada sloughs by 1 M HCl and 1 M NaOH treatment for demineralization and deproteinization, respectively. The brown color of this chitin from cicada sloughs was removed using 6% sodium hypochlorite as an oxidizing agent. It was found that the insect chitin extracted from the cicada sloughs has a higher percent recovery than the chitin from rice-field crab shells. The chemical structure and physicochemical properties of α-chitin from cicada sloughs were characterized using elemental analysis (EA), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), solid-state 13C cross-polarization magic-angle-spinning nuclear magnetic resonance (CP/MAS) NMR spectroscopy, X-ray diffractometry (XRD), and thermogravimetry (TG). The degree of acetylation (DA) was determined by EA, 1H NMR, and 13C CP/MAS NMR techniques. The DA values of chitin from cicada sloughs were in the range of 97% to 102% depending on each technique. Furthermore, it was found that the DA increased with an increasing thermal property and crystallinity.