The electron momentum spectroscopy of the inner valence orbitals 3a1 and 2b2 of methylene fluoride was studied by electron momentum spectroscopy(EMS). The experiment was performed using a high resolution(ΔE=1.15 eV FWHM,Δp=0. 1 a. u.)(e,2e)EMS spectrometer. The experimental momentum profiles of these two orbitals are compared with those calculated by Hartree-Fork method and Density Functional Theory.