Lead titanate (PbTiO3), a ferroelectric material with perovskite structure, has received a great deal of attention owing to a unique combination of its piezoelectric, pyroelectric, dielectric, electo- and acousto-optic properties [1–3]. PbTiO3 is a very attractive material for the use in a wide variety of fields, including ultrasonic sensors, infrared detectors, electro-optic modulators, and ferroelectric random access memories. To harness the intrinsic properties of PbTiO3 for device applications, however, high-quality epitaxial films are required. PbTiO3 thin films have been prepared by various methods such as chemical vapor deposition, rf magnetron sputtering, pulsed laser deposition, hydrothermal method, and sol-gel technique. Surprisingly, molecular beam epitaxy (MBE), with its precise control over composition, has not been widely applied, except of a few reports on MBE growth with the use of ozone as an oxidizing agent . In the present work, high-quality single-crystal PbTiO3 layers were grown on (001) SrTiO3 substrates by MBE with the use of hydrogen peroxide as an oxidant . Phase composition as well as structural and optical properties of the films were examined as a function of growth parameters by high-resolution x-ray diffractometry, spectroscopic ellipsometry, and photoluminescence. It was found that single-phase PbTiO3 films grew epitaxially at substrate temperatures above 600°C, whereas layers grown at lower temperature contained lead oxide inclusions. All the PbTiO3 layers were c-axis oriented with the epitaxial relationship PbTiO3(100)//SrTiO3(100) and PbTiO3//SrTiO3. No evidence of a-domains was found. Full width at half maximum of (001) rocking curves for 50–60 nm thick PbTiO3 layers are as low as 6–8 arcmin, indicating their good crystal quality. Pseudodielectric function of PbTiO3 was measured using variable angle spectroscopic ellipsometry at room temperature. Refractive index was found to be 2.605 at 633 nm (1.96 eV), which is consistent with the literature data. With the help of the standard critical point (SCP) lineshape analysis the band gap energy was calculated to be (3.778±0.005) eV.