The binding energy spectra and the momentum distributions of the valence orbitals of iso-butane, also known as methylpropane (CH3CH(CH3)CH3), are studied by using a high resolution binary (e, 2e) electron momentum spectrometer, at an impact energy of 1200eV plus the binding energy (8-32eV) with symmetric non-coplanar kinematics. Binding energy spectra of the valence shell are obtained at a coincidence energy resolution of 0.95 eV in full width at half maximum. The experimental momentum profiles of the inner valence orbitals are obtained and compared with the theoretical momentum distributions calculated by using Hartree-Fock and density functional theory methods with the basis sets 6-31G and 6-311++G**. The pole strengths of the inner orbitals are estimated and the final correlation effects are discussed.