We fabricated a core-cladding Ge–Sb–Se glass fiber with a Ge12.5Sb15Se72.5 core and Ge15Sb10Se75 cladding, achieved a supercontinuum spectrum spanning from 2 μm to 9 μm by pumping the Ge–Sb–Se fiber with a core diameter of 11 μm using a femtosecond laser pump at 3.8 μm, and numerically simulated the supercontinuum generation using the generalized nonlinear Schrödinger equation. In particular, we investigate the effect of the different Raman response functions that were calculated using the traditional single Lorentzian model and a multiple vibrational mode model on the evolution of the supercontinuum by comparing the supercontinua obtained from simulation and experimental results. We demonstrate that the Raman response function generated by the multiple vibrational mode model captures the actual response behavior of the material, and the supercontinuum generated using this model has more accuracy. To the best of our knowledge, this is the first reported study on supercontinuum generation in Ge–Sb–Se fiber utilizing a Raman response function calculated using the multiple vibrational mode model. This significant advancement enables more accurate simulation of supercontinuum generation in fibers with a multi-peaked structured Raman gain spectrum and holds great potential for optimizing the performance of various mid-infrared supercontinuum sources.