This article is devoted to the theory and experiment of the forced Rayleigh scattering method for measurement of thermal diffusivity of liquids which can be employed in the form of an instrument operated optically in a contact‐free manner. The theoretical considerations included are: (1) effect of cell wall, (2) effect of dye, (3) effect of Gaussian beam intensity distribution, (4) effect of heating duration time, and (5) effect of coupled dye and wall for a heavily absorbing sample. The errors caused by inadequate setting of optical conditions are also analyzed: (1) effects of grating thickness and (2) effects of initial temperature amplitude. Experimental verifications of the theory have been carried out through the measurements on toluene and water as standard reference substances. As a result of these experiments and theory, the criteria for optimum measuring conditions became available. To demonstrate the applicability of the present theory and the apparatus, the thermal diffusivities of toluene and methanol have been measured near room temperature under atmospheric pressure. The accuracy of the present measurement is estimated to be ±3%.