Based on degenerate four-wave mixing (FWM), the broadband Stokes waves are efficiently generated at the mid-infrared wavelength above 2 μm, for the first time to our knowledge, by coupling the femtosecond pulses into the fundamental mode of a silica photonic crystal fiber designed and fabricated in our laboratory. Influences of the power and wavelength of pump pulses on the phase-matched frequency conversion process are discussed. When pump pulses with central wavelength of 815 nm and average power of 300 mW are used, the output power ratio of the Stokes wave generated at 2226 nm and the residual pump wave P(s)/P(res) is estimated to be 10.8:1, and the corresponding conversion efficiency η(s) and bandwidth B(s) of the Stokes wave can be up to 26% and 33 nm, respectively. The efficient and broadband Stokes waves can be used as the ultrashort pulse sources for mid-infrared photonics and spectroscopy.