The laser-driven flyer plate is an important loading technology in high energy physics, shock wave physics, and explosive initiation application. How to generate a high-velocity and intact flyer plate by using the laser is a matter of concern for laser driving. In this study, the multilayer flyer plates (MFPs) of Al/Al₂O₃/Al and TiO₂/Al/Al₂O₃/Al with adjustable performance were designed and fabricated by magnetron sputtering and analyzed by scanning electron microscopy (SEM), laser reflectance spectrometer, and differential thermal analysis (DTA). The effects of the structure and material on the output performance of MFPs were analyzed by photon Doppler velocimetry (PDV) and ultrahigh-speed video. The morphology results showed that the structure of MFPs had uniform and clear boundaries between side-by-side layers. The MFP velocity was controlled in the range of 4.0–6.0 km/s by adjusting the film thickness, structure, and thermite material with 43.1 J/cm² laser ablation. Among them, the energetic flyers with the thermite ablation layer had the highest final velocity of 5.38 km/s due to the prestored energy of TiO₂/Al. By appropriately increasing the thickness of Al₂O₃ from 0.4 μm to 0.8 μm, the complete flight of the flyer plate to 3.72 mm can be realized. In addition, TiO₂/Al thermite film had characteristics of reaction heat release and lower laser reflectivity (72.13%) than the Al layer (80.55%), which explained the velocity enhancement effect of energetic flyer plates. This work provides facile strategy to enhance the output performance of MFPs, which may facilitate the practical applications of laser driving technology.