This study evaluates the effectiveness of a silica preceramic polymer for joining and coating Plasma Electrolytic Oxidated (PEO) aluminum components at temperatures below 200 °C. PEO aluminum slabs were coated and joined with a silica precursor polymer (Durazane1800, Merck, Darmstadt, Germany), both with and without the addition of 48 wt% silica nanoparticles, and cured at 180 °C for 4 h in air. Thermogravimetric analysis assessed the curing process and thermal stability, while X-ray diffraction confirmed the polymer’s conversion to amorphous silica after heating at 1200 °C. Resistance to humid environments was tested by soaking coated samples in tap water for a week, with no mass variation observed. Mechanical testing through tensile mode and tensile lap tests showed that adding 48 wt% silica nanoparticles significantly improved joint cohesion and nearly quadrupled mechanical strength. Fracture surfaces were examined using Field Emission Scanning Electron Microscopy, and composition analysis was performed with Energy Dispersion X-ray Spectroscopy. Crack detection was conducted using Computer Tomography with an in situ bending test setup to obtain the mechanical resistance of the PEO coating. The results indicate that the silica preceramic polymer is suitable for joining and coating PEO aluminum components, with silica nanoparticles enhancing mechanical strength and providing excellent thermal stability and resistance to humidity.