In this study, all‐optical organic–inorganic hybrid waveguide switches are proposed based on the photothermal effect of Au‐MOF composites. The embedded waveguide structure is directly defined using SiO2 grooves on a silicon substrate. Self‐synthesized Au‐MOF/PMMA and SiO2‐TiO2 network grafting PMMA are used as the core and cladding materials, respectively. The organic–inorganic hybrid shielding layer is formed using an oxygen ion etching process to avoid corrosion from the cladding solvent. A directional coupling switching structure is designed and fabricated. The switching time of the all‐optical device is 500 µs, the photothermal tuning sensitivity is 19.10 nm mW−1, the driving optical power consumption is 0.67 mW, and the extinction ratio is close to 9.83 dB. This technique is desirable for photothermal control of light in an all‐optical signal‐processing network.