A series of boron nitride (BN) composites, with different BN content, were prepared and characterized by cationic curing of DGEBA/BN formulations. As cationic initiator a commercial benzylanilinium salt was used. This cationic system shows good latent characteristics that were not lost on adding the filler. The performance of the catalytic system was optimized by varying the amount of initiator and adding little proportions of glycerol. The kinetics of the curing process was evaluated by calorimetric measurements. The addition of BN allowed increasing thermal conductivity without loss of mechanical properties like Young modulus, impact resistance, adhesion and other thermal characteristics like Tg or thermal stability. In addition, dielectric properties were improved with the increment of filler.