Multicolored optical switching phenomena are crucial for a broad range of applications, such as telecommunications and optical computing. However, most materials typically exhibit single-colored optical nonlinearity under intense laser illumination. Herein, our femtosecond time-resolved transient transmission measurements reveal the coexistence of the transient Pauli blocking effect in both the and valleys following intense optical excitation in films, demonstrating their feasibility as multicolored optical switching materials based on multivalley scattering. Additionally, a split-off energy of 240 meV at the point, attributed to the spin-orbit coupling effect, is directly observed from time-resolved transient transmission spectra. Based on an accurately calculated band structure, a scheme has been developed to interpret pump-probe transient transmission traces, effectively avoiding overinterpretation of overlapping transient signals caused by multiple-transition pathways. Furthermore, analysis of transmission transients using a three-level model indicates that the intervalley scattering time between the and valleys is within 196 fs, and the intravalley scattering time is within 1.10 ps in the valley, highlighting the potential for achieving an ultrafast multicolored optical switching device for key applications in multiband communications and optical computing.