A layered titanium(iv)-peroxo-pyridine dicarboxylic cluster K9[Ti3O4(O2)3(C7H3O4N)3(OH2)2]Cl·4H2O 1 has been synthesized by the H2O2-assisted reaction between TiCl4 and dipicolinic acid ligands. The semiconducting properties of this solid state compound were revealed from measurements of the diffuse reflectance UV-vis spectra and photocurrent response. Its photoelectrochemical sensing of dopamine was also investigated.