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Novel chalcogenide glasses of pseudo-binary (100?x)Sb2S3-xCuI systems were synthesized by traditional melt-quenching method. The glass-forming region of Sb2S3-CuI system was determined ranging from x=30 mol％to 40 mol％. CuI acts as a non-bridging modifier to form appropriate amount of [SbSI] structural units for improving the glass-forming ability of Sb2S3. Particularly, as-prepared glassy sample is able to transmit light beyond 14 μm, which is the wider transparency region than most sulfide glasses. Their physical properties, including Vickers hardness (Hv), density (ρ), and ionic conductivity (σ) were characterized and analyzed with the compositional-dependent Raman spectra. These experimental results would provide useful knowledge for the development of novel multi-spectral optical materials and glassy electrolytes.