The formation of thermochemical laser-induced periodic surface structures (TLIPSS) on 400-nm Ti films deposited onto a glass substrate is investigated under irradiation by a femtosecond laser with a wavelength of 1026 nm, pulse duration of 232 fs, repetition rate of 200 kHz, and with different spot sizes of 4–21 μm. The optimal fluence for TLIPSS formation reduces monotonously with increasing the spot diameter in the range. It is found that the standard deviation of the TLIPSS period depends significantly on the beam size and reaches approximately 2% when the beam diameter is in the range of 10–21 μm. In addition to TLIPSS formation with the main period slightly smaller than the laser wavelength, an effect of TLIPSS spatial frequency doubling is detected. The optical properties of TLIPSS (reflection spectrum and diffraction efficiency at different incident angles and polarizations) are investigated and compared with theoretical ones to give a basis for the development of an optical inspecting method. The refractive index and absorption coefficient of oxidized ridges of the TLIPSS are theoretically estimated by simulation of the experimental reflection spectrum in the zeroth diffraction order.