Leaves of Petunia inflata gave the following new steroids: (22R, 24S)-1α-acetoxy-24,25-epoxy-7α-hydroxy-22-nicotinoyloxyergost-11-en-3-one (petuniasterone B 22-nicotinate), (22R, 24S)-1α-acetoxy-7α,22-dinicotinoyloxy-24,25-epoxyergost-4-en-3-one (petuniasterone B 7,22-dinicotinate), (22R, 24S)-7α,22-diacetoxy-24,25-epoxyergosta-1,4-dien-3-one (petuniasterone C 7,22-diacetate), (22R, 24S)-24,25-epoxy-7α-hydroxy-22-nicotinoyloxyergosta-1,4-dien-3-one (petuniasterone C 22-nicotinate), (22R, 24S)-7α-acetoxy-24,25-epoxy-22-nicotinoyloxyergosta-1,4-dien-3-one (petuniasterone C 7-acetate-22-nicotinate), (22R, 24S)-7α,22-dinicotinoyloxy-24,25-epoxyergosta-1,4-dien-3-one (petuniasterone C 7,22-dinicotinate), (22R, 24R)-1α-acetoxy-7α,22,24,25-tetrahydroxyergost-4-en-3-one 22,24,25 orthoacetate (petuniasterone S), (22R, 24R)-1α-acetoxy-7α,22,24,25-tetrahydroxyergost-4-en-3-one 22,24,25 orthonicotinate (petunianine C). Those compounds having 1α-acetoxy groups are easily converted into the A-ring dienones by mild base. Orthoester and other side chain derivatives may be formed from the 24,25-epoxides upon acid treatment.