The development of well defined nanostructured thermosets from epoxy/PS-b-P2VP blends are presented in this study. For this purpose an epoxy system constituted by an epoxy resin (Araldite LY556), an anhydride hardener (Aradur 917), and an imidazole accelerator (DY 070) was employed and a block copolymer of PS-b-P2VP, where the block length of poly (2-vinylpyridine) (P2VP) was selected to allow the formation of microphase separated PS block nanodomains. Different ratios of PS-b-P2VP and epoxy system were used to analyze the nanostructuration of the system. Samples were characterized by transmission electron microscopy (TEM), fourier transform infrared, thermogravimetric analysis, and differential scanning calorimetry (DSC). DSC indicated that depletion of T-g occurred when concentration of block copolymer increased in the blend. TEM images showed vesicles and well defined cylindrical and lamellar nanostructured thermoset materials which were obtained when the PS-b-P2VP content was higher than 20 wt%.