A new route to prepare nanostructured thermosets by the utilization of intermolecular hydrogen-bonding interactions is demonstrated here. In this study, competitive hydrogen-bonding-induced microphase separation (CHIPS) in epoxy resin (ER) containing an amphiphilic block copolymer poly(e-caprolactone)-block-poly(2-vinyl-pyridine) (PCL-b-P2VP) is investigated for the first time. The phase separation takes place due to the disparity in the hydrogen-bonding interactions in ER/P2VP and ER/PCL pairs leading to the formation of ordered nanostructures in the ER/block copolymer blends. SAXS and TEM results indicate that the hexagonally packed cylindrical morphology of neat PCL-b-P2VP block copolymer remains but becomes a core shell structure at 10 wt % addition of ER, and changes to regular lamellae structures at 20-50 wt % then to disordered lamellae with 60 wt % ER. Wormlike structures are obtained in the blends with 70 wt % ER, followed by a completely homogeneous phase of ER/P2VP and ER/PCL. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen-bonding interactions between each component block copolymer and the homopolymer. This versatile method to develop nanostructured thermosets, involving competitive hydrogen-bonding interactions, could be used for the fabrication of hierarchical and functional materials.