The loss of chalcogenide microstructured optical fibers (ChG-MOFs) is generally higher than that of step fibers, mainly due to the immature fiber preform preparation method and strong waveguide defect scattering. Chemical polishing is used to polish mechanically drilled preforms to prepare ChG-MOFs with low defect scattering. Firstly, the scattering loss caused by the defective layer of ChG-MOFs is studied theoretically and experimentally. Then, a single-mode photonic crystal fiber (PCF) was prepared to verify the effect of chemical polishing on reducing fiber loss. The experimental results show that the PCF average loss is reduced from more than 8 dB/m to less than 2 dB/m, and the minimum loss reaches 0.8 dB/m @ 2.7 µm. At the same time, the bending strength of the PCF after chemical polishing is also significantly improved.