Mesophase pitch is an important starting material for making a wide spectrum of industrial and advanced carbon products. It is produced by pyrolysis of petroleum residues. In this work, mesophase formation behavior in petroleum residues was studied to prepare environmentally-benign mesophase pitches, and the composition of petroleum residues and its influence on the mesophase formation was investigated. Two petroleum residues, i.e., clarified oils (CLO-1, CLO-2) obtained from fluid catalytic cracking units of different Indian petroleum refineries, were taken as feed stocks. A third petroleum residue, aromatic extract (AE), was produced by extraction of one of the CLO-1 by using N-methyl pyrrolidone solvent. These petroleum residues were thermally treated at 380°C to examine their mesophase formation behavior. Mesophase pitches produced as a result of thermal treatment were characterized physico-chemically, as well as by instrumental techniques such as Fourier-transform infrared spectroscopy, nuclear magnetic resonance, X-ray diffraction and thermogravimetry/derivative thermogravimetry. Thermal treatment of these petroleum residues led to formation of a liquid-crystalline phase (mesophase). The mesophase formation behavior in the petroleum residues was analyzed by optical microscopy. Mesophase pitch prepared from CLO-2 exhibited the highest mesophase content (53 vol%) as compared to other mesophase pitches prepared from CLO-1 and AE.