The paper presents the results of investigation of changes in the composition of hydrocarbons and sulfur-containing compounds of an atmospheric residue in the course of cracking in the presence of a tungsten carbide–nickel–chromium (WC/Ni–Cr) catalytic additive and without it. The cracking is carried out in an autoclave at 500 °C for 30 min. The addition of the WC/Ni–Cr additive promotes the deepening of reactions of destruction not only of resins and asphaltenes, but also high molecular weight naphthene-aromatic compounds of the atmospheric residue. It is shown that the content of low molecular weight C9–C17 n-alkanes and C9–C10 alkylbenzenes rose sharply in the products of cracking with addition of WC/Ni–Cr in comparison with those produced without the additive. Alkyl- and naphthene-substituted aromatic hydrocarbons of benzene, naphthalene, phenanthrene series, polyarenes, benzo- and dibenzothiophenes are identified.