Extinction ratio (ER) is one of the important parameters to characterize the polarization‐maintaining (PM) performance of the fiber. In this paper, we report the preparation and properties of a novel chalcogenide microstructure fiber with a high ER. We fabricate a preform using a peeled‐off extrusion method. The core and cladding material of the fiber are Ge9As23Se68 and Ge10As22Se68. The preform was drawn into a fiber with an average ER of −17.08 dB. The loss of the fiber is less than 2 dB over 5.20–8.55 μm, and the minimum loss of the fiber is 0.57 dB/m at 6.2 μm. Moreover, a flat mid‐infrared supercontinuum spectrum spanning from 1.53 to 12.50 μm is generated by pumping an 18‐cm‐long PM fiber for the first time. [ABSTRACT FROM AUTHOR]