Pd/SiC Schottky diode has triggered interest as a chemical sensor to be operated at high temperatures. Various surface compounds formed at high temperatures are known to alter the device performance. In this work, the carbon and silicon related compounds and morphology of Pd ultra-thin film on 6H-SiC and 4H-SiC are investigated after thermal annealing using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The Pd ultra-thin films of about 3 nm in thickness are deposited by RF sputtering. The XPS analysis reveals the presence of silicon oxycarbides (SiCxOy) as deposited. After being annealed above 300°C, the atomic ratio of C to 0 in SiCxOy decreases with increasing the annealing temperatures, and the Pd film becomes a Pd silicide nanofeatured layer on SiC. When the annealing temperature is at 500°C, the majority of the SiCxOy is converted into SiO2. An amorphous Si phase exists after annealing at 200 to 400°C, which indicates that the Si-C bonds in SiC are broken at lower temperatures due to the presence of Pd. Graphite and C=O are found on the as deposited samples and also after annealing at temperatures up to 600°C. The formations of the carbon and silicon related compounds on Pd/4H-SiC are very similar to those on Pd/6H-SiC.