We study the interaction of acetone molecule $[(CH_3)_2CO]$ on Si(001) surface using density functional theory. An acetone molecule is adsorbed on a Si atom of the Si dimer of the Si(001) surface. The adsorption of the acetone molecule on the Si atom at lower height between the two Si atoms of the dimer is more favorable than that on the Si atoms at upper height. Then we calculate an energy variation of dissociation and four-membered ring structures of the acetone molecule adsorbed on the Si surface. Total energy difference between the two structures is about 0.05 eV, indicating that the two structures are almost equally stable. Energy barrier exists when a hydrogen atom is dissociated and adsorbed on the other Si atom of the dimer, while energy barrier does not exist when the adsorbed acetone molecule changes to four-membered ring structure, except for the rotation of the acetone molecule along z-direction. Therefore, four-membered ring structure is kinetically more favorable than the dissociation structure when the acetone molecule is adsorbed on the Si(001) surface.