Coupling of a phase transition to electron and phonon transports provides extra degree of freedom to improve the thermoelectric performance, while the pertinent experimental and theoretical studies are still rare. Particularly, the impaction of chemical compositions and phase transition characters on the abnormal thermoelectric properties across phase transitions are largely unclear. Herein, by varying the Cu content x from 1.75 to 2.10, we systemically investigate the crystal structural evolution, phase transition features, and especially the thermoelectric properties during the phase transition for CuxSe. It is found that the addition of over-stoichiometry Cu in CuxSe could alter the phase transition characters and suppress the formation of Cu vacancies. The critical scatterings of phonons and electrons during phase transitions strongly enhance the Seebeck coefficient and diminish the thermal conductivity, leading to an ultrahigh dimensionless thermoelectric figure of merit of～1.38 at 397 K in Cu2.10Se. With the decreasing Cu content, the critical electron and phonon scattering behaviors are mitigated, and the corresponding thermoelectric performances are reduced. This work offers inspirations for understanding and tuning the thermoelectric transport properties during phase transitions.