Chemical investigation of the deep-sea-derived fungus Rhizopus sp. W23 resulted in the identification of six new (1–3, 6, 8, 9) and 12 known (4, 5, 10–19) cyclocitrinol analogues, together with one handling artifact (7), all featuring an unusual 7/7/6/5-tetracyclic scaffold and bicyclo[4.4.1] A/B rings. Norcyclocitrinoic acids A and B (1, 2) represent the second occurrence of 24,25-bisnor cyclocitrinols. Structures were assigned to new steroids on the basis of extensive spectroscopic analysis and X-ray crystallography. Compound 13 significantly enhances osteoblastogenesis and inhibits adipogenesis in mature bone marrow stromal cells at 5 μM, indicating a potential to be an antiosteoporosis lead.