A novel all-inorganic aqueous sol–gel process has been developed to fabricate LaFeO3 thin films by dip-coating. Stable, positively charged colloidal sol particles of hydrous lanthanum ferrite with an average particle size (Z av ) of 7 nm were prepared and coated onto quartz plates under controlled conditions. The sols have been characterized using photon correlation spectroscopy (PCS) for Z av and size distribution. The redispersible gel was characterized by thermogravimetric and differential thermal analysis (TG-DTA) and also by isothermal heating followed by X-ray diffraction to identify the reaction sequence to form LaFeO 3. The sol–gel films as deposited were X-ray amorphous on heating up to 500°C, partially crystalline at 600°C, fully crystalline and single phase at 650°C and above. These films were continuous, polycrystalline, single phase, had uniform thickness in the range between 180 to 1000 nm, depending on deposition conditions, and showed about 80% optical transmittance. The optical band gap varied from 2.7 to 3.3 eV as a function of the annealing temperature. The refractive index increased with increase in annealing temperature from 1.55 at 500°C to 1.86 at 800°C.