Ustilobisorbicillinol A (1), which is a novel bisorbicillinoid featuring a unique cage structure that incorporates one sorbicillinol and one sorbyl-containing phenanthrenone unit, was isolated from the culture of Ustilaginoidea virens. Three biogenetically related new metabolites (2-4) were also isolated. Their structures were elucidated by extensive spectroscopic analyses, including the 13C NMR and electronic circular dichroism (ECD) calculations for the configurational assignment. The biosynthetic pathway for these sorbyl-containing polyketides was proposed. Compound 1 showed pronounced cytotoxicity, and it induced significant cell cycle arrest and apoptosis.