High-quality c-axis-oriented Ca3Co4O9+δ thin films have been grown directly on Si (100) wafers with inserting MgO buffer layers by pulsed-laser deposition (PLD). X-ray diffraction and scan electron microscopy show good crystallinity of the Ca3Co4O9+δ films. The resistivity and Seebeck coefficient of the Ca3Co4O9+δ thin films on Si (100) substrates are 9.8 mΩcm and 189 μV/K at the temperature of 500K, respectively, comparable to the single-crystal samples. This advance demonstrates the possibility of integrating the cobaltate-based high thermoelectric materials with the current state-of-the-art silicon technology for thermoelectricity-on-a-chip applications.