In this study, carbon fiber/epoxy composites (CFRP) were fabricated by vacuum‐assisted resin infusion molding (VARIM) with polyphenylene ether (PPE) as a toughening agent. The PPE contained hydroxyl end groups that facilitated chemical bonding with epoxy during curing. PPE was incorporated into the epoxy matrix by dissolution, and spreading in the interlaminar regions. The presence of PPE as a toughener exhibited significant improvement in the Mode‐I fracture toughness of the composites. The CFRP samples, which were toughened with 5 wt.% and 10 wt.% PPE, showed about 191% to 380% enhancement, respectively, in the critical energy release rate (GIC) compared to the unmodified sample. Dynamic mechanical analysis (DMA) showed about a 6°C increase in the glass transition temperature of the toughened composites, which is an interesting aspect of this work. These results indicate the potential of using PPE as a toughening agent in CFRP composites.