A novel diterpenoid with an unprecedented 5/6/5/7 tetracyclic system, rhodauricanol A (1), five new grayanane-derived diterpenoids, dauricanols A−E (2−6), and five known ones (7−11) were isolated from the flowers of Rhododendron dauricum. Rhodauricanol A (1) possesses a unique 5/6/5/7 tetracyclic ring system featuring a 16-oxa-tetracyclo[11.2.1.0^1,5.0^7,13]hexadecane core. Dauricanols A−C (2−4) are the first 1,3-dioxolane conjugates of grayanane diterpenoids and 5-hydroxymethylfurfural and vanillin, respectively, and dauricanols D (5) and E (6) represent the first examples of 6-deoxy-1,5-seco-grayanane diterpenoids. Their structures were determined by spectroscopic methods, quantum chemical calculation including ¹³C NMR-DP4+ analysis and ECD calculation, and single-crystal X-ray diffraction analysis. Plausible biosynthetic pathways for 1−4 were proposed. All the isolates showed significant analgesic activities, and dauricanols B (3) and C (4) showed more potent analgesic activities than the positive control, morphine.