Dear Student,
No, gamma rays cannot be emitted from excitation or de-excitation of electrons. Gamma rays are emitted by the excited atomic nuclei. It consists of high energy photon. These rays are of smallest wavelength and most energy of any wave in the electromagnetic spectrum.
Decay of an atomic nucleus from a higher energy state i.e. excited state to lower energy state i.e. ground state produces gamma rays. This process is called as gamma decay.