Five new hispidin derivatives, phaeolschidins A-E (1-5), as well as two known natural products, pinillidine (6) and hispidin (7), were isolated from the fruiting bodies of Phaeolus schweinitzii collected in the Tibetan Plateau. The structures of the new compounds were elucidated by spectroscopic methods. Phaeolschidins A-D (1-4) are new bishispidins. Phaeolschidin E (5) is a new class of hispidin derivative in which one pyrrolidin-2-one moiety was linked to C-3 of hispidin. The antioxidant activity of 1-7 was evaluated using three methods: the DPPH scavenging assay, the total antioxidant capacity assay, and the lipid peroxidation assay. Hispidin showed the strongest antioxidant activity of all tested compounds. This is the first report of secondary metabolites from the fungus P. schweinitzii.