We simulate a relaxation process of a polaron in polymer after photo excitation, and a new state is realized by means of proper excitation. The original lattice configuration of the polaron splits into two symmetrical peaks,and consequently a double-well potential is formed, where the wavefunctions of electron localized in these two wells are entangled. Thus, this process provides a method to generate the Schrodinger cat state. According to the dynamical process of the lattice configuration, the relaxation time of splitting is about 150fs.