Bioenergy out of lignocellulosic biomass, especially from agricultural crop residues, is making massive inroads in our quest for sustainable environment. In the present study, detailed physico-chemical characterization, thermal degradation characteristics, and kinetics of pyrolysis of corn cob are reported. Thermogravimetric experiments were performed at different heating rates, such as, 10, 20, and 30 °C/min in an inert atmosphere. Thermogravimetric (TG) and derivative thermogravimetric (DTG) curves inferred the thermal behavior characteristics of corn cob. Significant content of cellulose and hemicellulose put together (76.23%) suggested tremendous potential of corn cob to give enhanced yield of bio-oil through pyrolysis. Maximum mass loss of 61.92% for corn cob was observed in the temperature range of 180–360 °C. The kinetic parameters for pyrolysis of corn cob were determined by employing model-free isoconversional methods like, Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Starink. Activation energy from FWO (62.44 kJ/mol) and Starink (61.74 kJ/mol) method for pyrolysis of corn cob was found to be in close proximity. The results revealed prospective bioenergy potential of corn cob as a feedstock for pyrolysis process.