Birefringent microstructure fibers are shown to allow efficient gereration of anti-Stokes line emission as a result of four-wave-mixing in higher mode by using unamplified femtosecond Ti:sapphire laser pulses.Intense blue-shifted lines with different central wavelength were generated in the high-delta (i.e.high-air filling in the cladding) microstructure fiber with axis sizes 50 and 46 μm by femtosecond laser pulses with 35-fs in duration,820nm in central wavelength and 4nJ in energy per pulse.The experimental result shows that phase-matched four-wa ve mixing in higher-order modes of microstructure fibers allows unprecedentedly high efficiencies of anti-Stokes frequency conversion to be achieved for subnano joule femtosecond laser pulses.The dependence factor of the four waves mixing in birefringent microstructure fiber is compared and analyzed.Good agreement betwe en the theory and experiment is achieved.