A reversible structural transition of an epitaxial La(2/3)Sr(1/3)MnO3 film deposited on a LaAlO3 substrate has been investigated by means of in situ high-resolution transmission electron microscopy and electron diffraction, combined with image and diffraction calculations. We observe that the crystallographic symmetry of the film can be lowered via electron beam irradiation, leading to a rhombohedral-monoclinic transition. This transition can be attributed to the cooperating effect of the mismatch stress and the irradiation-induced thermal stress.