Novel thermoresponsive hybrid inorganic/organic thermosetting materials based oil hydrophobic titanium dioxide nanoparticles and amphiphilic poly(styrene-b-ethylene oxide) block-copolymer-dispersed 4'-(hexyl)-4-biphenyl carbonitrile liquid crystals were prepared and characterized. The obtained results confirm that these multiphase materials maintain thermo-optical properties of incorporated liquid crystals and show good dispersion of the titanium dioxide, which the microphase separated within the HBC/PS-block. Moreover, well-dispersed nanoparticles spontaneously form well-defined highly dense arrays of titania nanodots located in the interface between the epoxy matrix and the microphase-separated HBC/PS-block, which, combined with the fact that TiO2 nanoparticles maintain their conductive properties in the investigated systems, can lead to the generation of novel materials with interesting specific properties.