A numerical study was realized in order to simulate the plasma spraying of a Mo/NiCrBSi powder mixture under atmospheric conditions. The influence of the spray parameters on particles' in-flight characteristics was investigated numerically. The PHOENICS CFD code was used for the computation of the plasma jets and an in-house code was developed for the modeling of plasma/particles interactions. In view of the high melting temperature of Molybdenum and the presence of a self fluxing alloy like NiCrBSi, the state of the Mo particles prior to their impact on the substrate (velocity, temperature) was regarded as one of the major element influencing the quality of the produced coatings. Different spray parameters were considered: the plasma gas was an argon/hydrogen mixture with two different total flow rates and three different hydrogen fractions. Corresponding experiments are presented and appear to be consistent with numerical results.