We theoretically investigated the ultrafast thermal excitation behaviors on Au films surface irradiated by polarization-shaped femtosecond laser. The spatio-temporal dynamics of temperature evolution in Au film with polarization-shaped femtosecond laser excitation are obtained based on Finite Element Method (FEM). It is revealed that the phonon temperature fields can be flexibly adjusted by optimizing the polarization state combinations of polarization-shaped double femtosecond laser pulses. The results are attributed to pulse synthetic effect, which closely depends on the polarization state combinations of double femtosecond laser pulses. The study provides the basic for understanding of the thermal excitation dynamics for optimizing laser micro and nano-fabrications via tailoring the polarization state of temporally shaped femtosecond laser.