Thermolysis of N-phenyl, N-para-biphenyl, and N-para, para′-terphenylmaleimide with 7-dehydrocholesteryl acetate in benzene solution at 200 °C yields mixtures of four cycloadducts in relative yields that are essentially independent of the maleimide substituent. The three major products are those of ene addition to C7 of the steroid with abstraction of the proton at C9 or C14. The α-endo-Diels-Alder adduct is formed as a minor product. The structures of the adducts have been elucidated on the basis of one- and two-dimensional 1H and 13C NMR spectroscopic techniques, including homonuclear 1H decoupling, NOE, 1H–1H COSY, heteronuclear 1H–13C shift correlation, and TOCSY 2-D experiments, and the results of molecular mechanics (MMX) calculations. The combination of these techniques has made it possible to almost completely assign the 1H and 13C NMR spectra for two of the ene adducts and the Diels–Alder adduct from reaction of 7-dehydrocholesteryl acetate with N-phenyl maleimide.