The diamond photonic crystals with the periodic arrangement of high dielectric constant (ε=100) were fabricated, and photonic band gap properties in the millimeter waveguides were investigated. Acrylic diamond lattice structures with TiO2 dispersion at 40 vol. % were fabricated by Micro-stereolithography. The forming accuracy was 10m. After sintering process, TiO2 diamond lattice structures are obtained. The relative density reached 96%. The millimeter wave transmittance properties were measured with network analyzer and W-band millimeter waveguide. The band gap was measured between 90 GHz and 110 GHz in the Γ-X <100> direction, which was well agreed with the results calculated by the plane wave expansion method and simulated by the Transmission Line Modeling method.