The influence of carbon nanotube (CNT) modification on the dispersion and localization behavior of the CNTs in immiscible blends of polystyrene (PS) and polybutadiene (PB), and in the nanostructured morphology of a star-shaped styrene-butadiene based block copolymer (BCP), was studied to form a basis for the development of functional materials with defined electrical property profiles. Unmodified multi-walled CNTs (MWCNTs) were dispersed in PS, PB and PS/PB blends by solution mixing. Additionally, MWCNTs were functionalized with n-octadecylamine and monoamino-terminated polystyrene to increase the compatibility between the homopolymers and the nanofiller. The MWCNT dispersion and the blend morphology formation were studied using transmission light microscopy and scanning electron microscopy. The MWCNT dispersion could be significantly improved by the modification of the MWCNTs. All MWCNT types were found to preferably localize in the PS phase of the PS/PB blend. However, only blends containing unmodified MWCNTs were electrically conductive. Similar effects were found in BCP/MWCNT composites. The BCP was already electrically conductive with a filler content of 0.1 wt % of unmodified MWCNTs. The stress–strain behavior of the BCP was slightly influenced by MWCNT addition and CNT modification. The dispersability of MWCNTs was significantly improved by CNT functionalization, which indicates a strong polymer-filler interaction.