The major constituent of the alkaloid fraction of the leaves of Paravallaris macrophylla Pierre has found to be the new paravallarine‐type steroidal alkaloid 20‐epi‐kibataline. The structure of this steroidal alkaloid has been determined by X‐ray analysis. The compound crystallizes in the monoclinic space group P21 with the lattice parameters a = 11.286, b = 14.250, c = 6.206 Å, β = 97.88°. The final R value was 0.067. Copyright © 1985 WILEY‐VCH Verlag GmbH & Co. KGaA