Several petroleum pitches have been prepared by thermal treatment of various petroleum-derived residues such as clarified oil, aromatic extract and pyrolysis tars. These pitches were characterized physico-chemically (softening point, coking value, QI, & TI) and instrumentally (NMR) and compared. Attempts have been made to correlate physicochemical properties of petroleum residues and pitches with their NMR structural parameters through regression analysis. Studies on high temperature in-situ 1H NMR analysis of pitches have also been carried out. Structural characterization of petroleum residues and pitches is very useful for screening of petroleum residues and optimization of process variables for tailoring pitch properties for different end-use applications.