Thirteen new sesquiterpenoids, including six guaiane type auranticanols A–F (1, 2, and 4–7) and seven carotene type auranticanols G–M (18–24) were isolated from the stems of Daphne aurantiaca Diels., along with fourteen known sesquiterpenoids (3, 8–17, 25–27) and two known tigliane diterpenoids (28, 29), and their structures were elucidated by extensively analyzing their MS and NMR spectroscopic data. A bioassay of anti-HIV activity indicated that compounds 11, 14, 19, and 28 showed definite activities with EC₅₀ values of 2.138, 0.286, 1.773 and 0.000282 μg mL⁻¹ and SI > 93.545, 93.787, 10.243, and 65 177.305, respectively.