Abstract: The electron momentum profile for inner valence orbitals 2b and 3a of cyclohexene (C6H10) was firstly studied by the binary (e,2e) electron momentum spectroscopy (EMS), at the impact energy of 1200 eV plus binding energy using symmetric non-coplanar kinematics. The complete valence shell binding energy spectrum of C6H10 was also obtained. The experimental momentum profile of the summed orbitals was compared with Hartree Fock (HF) and density functional theory (DFT) methods with various basis sets. The experimental measurement was well described by the HF and DFT calculations except for the low-p region (p<0.25 a.u.). Experimental small “turn-up” effects of momentum profile in the low-p region could be due to the distorted wave effects.