Two-color, toluene-based, planar laser-induced fluorescence (PLIF) is utilized to characterize the thermal structure of a turbulent, free jet. The PLIF technique has been used to measure concentration gradients for combustion applications, but its use to quantify thermal gradients is limited. To validate the method, compressed air is seeded with toluene particles. The seeded airflow is heated to temperatures varying from 300 to 375 K, and the heated jet exits a 1.27-cm diameter orifice into quiescent, room temperature air. The jet Reynolds number is varied from 5000 to 15,000. As the jet exits the orifice, the toluene particles fluorescence across a 266 nm laser light sheet which ultimately provides a two-dimensional temperature distribution of the free jet. The rigorous calibration procedure for the PLIF technique is described along with the seeding nuances needed to quantify the thermal structure of the jets. The PLIF technique has been demonstrated for this fundamental flow field, and it has proven to be applicable to more complex heat transfer and cooling applications. Furthermore, the time-averaged temperature distributions obtained in this investigation can be used in the validation of turbulent computational fluid dynamics (CFD) solvers.