Conductive properties of different thermosetting materials modified with nematic 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) liquid crystal and rutile TiO2 nanoparticles were successfully studied by means of tunneling atomic force miscroscopy (TUNA). Taking into account the liquid crystal state of the H BC at room temperature, depending oil both the HBC content and the presence of TiO2 nanoparticles, designed materials showed different TUNA currents passed through the sample. The addition of TiO2 nanoparticlcs into the systems multiply the detected current if compared to the thermosetting systems without TiO2 nanoparticles and simultaneously stabilized the current passed through the sample, making the process reversible since the absolute current values were almost the same applying both negative and positive voltage. Moreover, thermosetting systems modified with liquid crystals with and without TiO2 nanoparticles are photoluminescence switchable materials as a function of temperature gradient during repeatable heating/cooling cycle. Conductive properties of switchable photoluminescence thermosetting systems based on liquid crystals can allow them to find potential application in the field of photoresponsive devices, with a high contrast ratio between transparent and opaque states.