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Organic-inorganic nanojunction can results in a selective scattering of charge carrier depending on their energy, which leads to a simultaneous increase in Seebeck coefficient S and power factor PF when the Fermi levels of the constituent materials are aligned appropriately. In this work, the nanojunction was successfully employed at the organic-inorganic semiconductor interface of polyparaphenylene (PPP) and Zn_1-xCo_xO nanoparticles through sol-gel method. The resulting Zn_0.925Co_0.075O/9 wt% PPP hybrids exhibited a high power factor due to the largest electrical conductivity and higher Seebeck coefficient. Moreover, organic-inorganic nano-interface effectively reduces the thermal conductivity by interface scattering of phonons. All these effects finally lead to a thermoelectric figure of merit, ZT up to 0.22 in these inorganic-organic nanocomposites, which corresponds to a 5-fold enhancement compared to that of the Zn_0.925Co_0.075O matrix. This work demonstrates the effectiveness of nanojunctions and provides a rational route to high performance thermoelectrics in a bulk material.