In the realm of optical component design, the proposed multilayer grating splitter represents a significant breakthrough. For the triple-layered grating in this paper, it combines the outstanding optical properties of polyvinylidene fluoride (PVDF), aluminum oxide (Al2O3), and gadolinium oxide (Gd2O3) to achieve high-efficiency outputs for both the 0th and −2nd orders under secondary Bragg angle incidence conditions. The diffraction efficiencies for both TE and TM polarizations exceed 97%, with energy uniformity surpassing 99%. These results highlight the potential of this design in precision beam control applications. The splitter's performance benefits from the intrinsic material properties and optimally designed structural dimensions, which enhance transparency and thermal stability under operational conditions. Through rigorous design and optimization, including modal methods and simulated annealing algorithms, the device achieves exceptional uniformity in diffraction efficiency, which is crucial for high-resolution spectroscopy and precision optical measurement applications.