In this work, novolac bisphenol‐F‐based vanadium–phenolic resin/modified zirconia (Bis‐VPF/m‐ZrO) composites were obtained successfully. In the preparation process, ammonium vanadate reacted with Bis‐PF resin to form Bis‐VPF resin with the VO chemical bonds. Simultaneously, zirconia (ZrO2) was modified with N‐(2‐aminoethyl‐3‐aminopropyl)trimethoxysilane (AEAPTMS). Then, this modified zirconia (m‐ZrO) was fully mixed with Bis‐VPF to form Bis‐VPF/m‐ZrO composites. The thermal properties and mechanical strength of Bis‐VPF are higher than those of Bis‐PF. When the m‐ZrO was additionally incorporated into Bis‐VPF, the well‐dispersed and well‐adhered m‐ZrO can further promote all the above‐mentioned properties of the composites. Furthermore, Bis‐VPF/m‐ZrO was compared with Bis‐PF in the performance as a binder for cBN grinding wheels. The results of grinding experiments indicated that Bis‐VPF/m‐ZrO is a better binding resin than Bis‐PF, and so the grinding wheels made from the Bis‐VPF/m‐ZrO composites have better grinding effect and quality. POLYM. COMPOS., 37:3354–3364, 2016. © 2015 Society of Plastics Engineers