Novel hybrid TiO 2 /(HOBC/PSEO) inorganic/organic materials based on hydrophobic rutile TiO 2 nanoparticles and low-molecular-weight 4′-(hexyloxy)-4-biphenyl carbonitrile (HOBC) liquid crystals confined on a self-assembled poly(styrene-b-ethylene oxide) (PSEO) block copolymer have been studied. HOBC liquid crystals surrounded TiO 2 particles, forming core–shell structures, resulting in selective location of nanoparticles in the PS-block of the PSEO block copolymer. Moreover, multiphase inorganic/organic materials maintained the electrical properties of the core TiO 2 nanoparticles after encapsulation in the HOBC/PS-block composite matrix. Depending on the composition of TiO 2 /(HOBC/PSEO) inorganic/organic hybrids, TiO 2 nanoparticles showed arrangement of nanodots in one of the self-assembled blocks.