High velocity oxy-fuel (HVOF) sprayed, functionally graded polyimide/WC-Co composite coatings on polymer matrix composites (PMC's) are being investigated for applications in turbine engine technologies. This requires that the polyimide, used as the matrix material, be fully crosslinked during deposition in order to maximize its engineering properties. The rapid heating and cooling nature of the HVOF spray process and the high heat flux through the coating into the substrate typically do not allow sufficient time at temperature for curing of the thermoset. It was hypothesized that external substrate preheating might enhance the deposition behavior and curing reaction during the thermal spraying of polyimide thermosets. An additional difficulty arises from the low thermal conductivity and low specific heat capacity of the PMC substrate, which prevent effective substrate preheating by the HVOF jet as in the case of metallic substrates. A simple analytical process model for the deposition of thermosetting polyimide onto polymer matrix composites by HVOF thermal spray technology has been developed. The model incorporates various heat transfer mechanisms and enables surface temperature profiles of the coating to be simulated, primarily as a function of substrate preheating temperature. Four cases were modeled: (i) no substrate preheating; (ii) substrates electrically preheated from the rear; (iii) substrates preheated by hot air from the front face; and (iv) substrates electrically preheated from the rear and by hot air from the front. Thermal properties of the polyimide needed for the simulations were determined by Differential Scanning Calorimetry (DSC) and Thermo-Gravimetric Analysis (TGA). Microstructural characterization of the coatings and the morphology of polyimide splats sprayed both with and without substrate preheating were analyzed using standard metallographic techniques. Coating temperature in cases (iii) and (iv) never dropped below the crosslinking temperature of the polyimide feedstock. This was the critical condition required for the curing reaction and successful deposition of thermosets by HVOF thermal spraying.