An novel organic-inorganic grafting polymethyl methacrylate (PMMA) material is successfully synthesized. Based on the preferable thermal stability and optical properties, the all-polymer thermo-optic(TO) waveguide switch chip at 650 nm wavelength is designed and fabricated. The chip is designed as embedded waveguide with reversed ridge structure for single-mode propagation of the red signal light. The polymer optical fiber (POF) is used for coupling the 650nm visible light into the chip for testing. The Mach-Zehnder (M-Z) interferometer TO switch on-off time is about 600 μs. The extinction ratio is about 8.2 dB and the applied electric power as the switching power is about 22.6 mW. This device can be widely used in many fields such as high density optical integration system, visible light communication and biochemical sensing technology, etc.