In order to study the thermoelectric properties of TiO2-based hybrid materials, TiO2/polyparaphenylene (PPP) nanocomposites are fabricated by spark plasma sintering (SPS). The results show that the electrical conductivity follow percolation theory is enhanced due to the electron transfer highway provided by the conducting PPP phase. Furthermore, the thermal conductivity is reduced due to the drastic difference of vibrational spectra between organic and inorganic components. As a result, the greatest ZT = 0.24 is obtained for TiO2/0.75 wt% PPP sample, which is 15-fold higher than pure TiO2 (ZT = 0.016).