Biofuels have been long term considered in blends with mineral diesel aiming to reduce particulate matter (PM) emissions in diesel engines. In this context, biodiesel is one of the most promising biofuels, although optimizer additives are also considered to further reduce PM emissions. This work presents the results of an evaluation of the particle number and size distribution (PSD) emitted by a diesel engine fueled with mineral diesel, biodiesel and an optimizing additive. This additive aims to reduce the number of particles emitted, which advantages the use of biofuel in a diesel engine. This comparative study has shown that the addition of biodiesel to mineral diesel induces an increase in peak PM emissions and the additive was able to reduce emissions for the biodiesel mixture within the engine conditions tested.