We report direct experimental determination of the wavefunction mixture and composition for hybridized Zeeman states of P in Si. The intensity evolution of the Zeeman transitions nearby anti-crossing region for the isolated P donors in high pure Si bas been measured quantitatively by use of high sensitive and high resolution photothermal ionization spectroscopy (PTIS); The wavefunction compositions and their evolutions upon magnetic field for the hybridized Zeeman states of bounded electrons of impurities have been deduced from the measurement. A variational calculation under the frame of effective mass approach has been performed to estimate theoretically the wavefunction composition. The results are campare with experimental ones.