A biobased diglycidyl ether of vanillin (DGEVA) epoxy resin was nanostructured by poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-PPO-PEO) triblock copolymer. Due to the miscibility/immiscibility properties of the triblock copolymer in DGEVA resin, different morphologies were obtained depending on the triblock copolymer amount. A hexagonally packed cylinder morphology was kept until reaching 30 wt% of PEO-PPO-PEO content, while a more complex three-phase morphology was obtained for 50 wt%, in which large worm-like PPO domains appear surrounded by two different phases, one of them rich in PEO and another phase rich in cured DGEVA. UV-vis measurements show that the transmittance is reduced with the increase in triblock copolymer content, especially at 50 wt%, probably due to the presence of PEO crystals detected by calorimetry.