We demonstrate microstructuring of chalcogenide fiber end faces in order to obtain enhanced transmission due to the antireflective properties of the microstructured surfaces. A variety of molding approaches have been investigated for As(2)S(3) and As(2)Se(3) fibers. Transmission as high as 97% per facet was obtained in the case of As(2)S(3) fiber, compared to the native, Fresnel-loss limited, transmission of 83%. The potential for hydrophobic character was also demonstrated by increasing the contact angle of water droplets to greater than 120°.