Cardanol-based epoxidized novolac vinyl ester resin (CNEVER) was synthesized by reacting cardanol-based epoxidized novolac (CNE) resin and methacrylic acid (MA) (CNE:MA molar ratio 1:0.9) in presence of triphenylphosphine as catalyst at 90°C. The CNE resin was prepared by the reaction of cardanol-based novolac-type phenolic (CFN) resin and epichlorohydrin, in basic medium, at 120°C. The CFN resin was synthesized by reacting cardanol (C) and formaldehyde (F) (C/F ratio=1:0.7) with p-toluene sulphonic acid (PTSA) as catalyst (0.5wt.%) at 120°C for 7h. The resin products were analyzed by Fourier-transform infra-red (FTIR) and nuclear magnetic resonance (NMR) spectroscopic analysis. The number-average molecular weight of the prepared CNEVER was found to be 859gmol −1 as determined by gel permeation chromatographic (GPC) analysis. The resin was cured by using the mixture of resin, benzoyl peroxide, and styrene at 120°C. The CNEVER resin was found to be cured in 60min at 120°C. Differential scanning calorimetric (DSC) technique was used to investigate the curing behaviour. Single step mass loss in dynamic thermogravimetric (TG) trace of CNEVER was observed. Thermal stability of the vinyl ester sample containing 40wt.% styrene was the highest amongst all other prepared systems.