Abstract Fluid catalytic cracking (FCC) feeds from four Indian refineries are structurally characterized by 1H, gated-decoupled 13C, distortionless enhancement by polarization transfer (DEPT) and 2D 1H– 13C HETeronuclear CORrelation (HETCOR) and other 2D nuclear magnetic resonance (NMR) methods. Detailed structural analyses are completely supported by a range of NMR information including chemical shifts of 1H and 13C, CH n type distributions and 1H – 13C connectivities. The average structural parameters like branching sites, average number of branching per molecule, average length of side chains, percentage of saturates, aromatics and naphthenes are obtained from these NMR data. A novel approach based on “multipoint spline base line correction” is employed for estimation of naphthenes and n-paraffins that gives better quantitative estimation than the conventional methods. In this paper, importance is given to the study of those structural parameters that plays a key role in cracking chemistry as well as coke forming tendency of the feedstock. To the best of our knowledge, this is the first attempt to characterize and quantitatively estimate compositions of the high boiling fractions of petroleum feed by NMR methods and especially the complex structure of vacuum gas oil (VGO) fractions used in Indian refineries. The importance of this paper is to help in optimizing the product slate of Indian refineries through proper feedstock blending using few hundreds of million metric tons (MMT) of crude oil consisting of blends of light crudes with different heavy crudes and bottom of the barrel due to escalating cost of crudes.