Abstract We have investigated two-photon polymerization of metal ions doped acrylate monomers and oligomers which is applied for three-dimensional (3D) micro/nano-structure fabrication. Titanium (IV) ions doped urethane acrylate photopolymerizable resins were synthesized, and their optical and polymerization properties were investigated. The resolution of two-photon polymerization for micro/nanofabrication was evaluated. Titanium dioxide (TiO 2) nanoparticles were generated in the polymer matrix of micron-sized polymer structures. A 3D diamond photonic crystal structure, which consisted of polymer composite materials of TiO 2 nanoparticles, was successfully fabricated by direct laser writing and its photonic bandgap was confirmed. This work would give us a new solution for producing 3D micro/nanodevices of functional polymer composite materials.