Local temperatures and amplitudes of their temporal fluctuations caused by instabilities of the reacting medium composition and of the combustion process itself were measured for turbulent diffusion combustion of decane–air vapor–gaseous mixtures in a flame of a laboratory burner using a coherent anti-Stokes Raman scattering diagnostic system with nanosecond pulse duration of the pump lasers and broad modeless spectrum of Stokes radiation. The relative error of thermometry of nitrogen-containing mixtures in the range 100–2000 K during one laser pulse (10 ns) was 3.1%.