The homogeneous charge compression ignition (HCCI) combustion process is an advanced operating mode for automotive engines. The self-ignition mechanisms that occur within the combustion chamber exhibit extreme temperature dependence. Therefore, the thorough understanding of corresponding phenomena requires the use of diagnostic methods featuring a sufficient thermal sensitivity, applicable in severe conditions similar to those encountered within engines. In this respect, toluene planar laser-induced fluorescence (PLIF) is applied to the inert compression flow generated within an optical rapid compression machine (RCM). A relatively simple diagnostic system is retained: a single wavelength excitation device (266 nm) and a single (filtered) collection system. This diagnostic system is associated with an image processing strategy specifically adapted to RCM devices. Despite the severe conditions under consideration (40 bar, 700–950 K), the method allows us to obtain relatively large two-dimensional temperature fields that display a level of description seldom achieved in such devices. In particular the temperature gradients, which play a crucial role in HCCI combustion processes, can be estimated. The present experimental results confirm the good reliability and accuracy of the method. The information gathered with this toluene PLIF method puts in evidence its high potentialities for the study of aero-thermal-reactive processes as they take place in real engine conditions. The retained strategy also brings new possibilities of non-intrusive analysis for flows practically encountered within industrial devices.