The theoretical model is proposed to describe the dynamics of localization of a shared electron in a pentamer nanocluster in the external low-frequency crossed electric fields, taking into account the electron-vibration interaction. When constructing this model, a semi-classical approach is used, in which a quantum description is applied to the electron subsystem, and the vibrational subsystem and the external electric field are described classically. Based on this model, a system of differential equations was obtained for the time dependences of the probability amplitudes of detecting an electron at different centers of the pentamer. This model is used to describe pentamers of planar-square and pyramidal configurations. For these two types of geometric configuration of pentamers, numerical calculations were carried out at different values of model parameters. The proposed model is characterized by the fact that the centers of the nanocluster are considered as weakly tunnel-coupled, and the electron-vibration interaction with the ligand environment at each of its centers plays a significant role. In this case, tunneling is taken into account only between the nearest centers of the nanocluster, and the centers themselves considered together with their ligand environment are considered equivalent. The controlling role of the external electric fields has been revealed, which consists in the fact that variations in its frequency and intensity amplitude allow the implementation of various regimes of electron localization in a pentamer nanocluster.