In the present work, the silanized hybrid fillers of nano/micro glass fiber (nGF) and coal fly ash (CFA) were synthesized and used as additives for vinyl ester resin reinforced with carbon fiber (CFRV). The silane characteristics agent with the vinyl group was used to coat in the surface of additives by applying the silanization processing. The sheet molding compound (SMC) method and two steps hot curing processing were applied to receive the CFRV. The results pointed out that the using of silanized hybrid fillers of nGF and CFA with weight ratio of 0.1/1 helps to enhance the performances of the CFRV. Compared with pristine sample, the mode I interlaminar fracture toughness (GIC), the tensile strength, impact strength of CFRV were improved by 48.61%; 61.39%; and 56.82%, respectively. The de-bonding of fillers from the matrix from the SEM observation was considered as reason for improvement of fracture toughness of CFRV.