A new chiro-inositol ester, 4-hydroxyphenylacetyl-3-d-chiro-inositol ester (1), was isolated from the whole plants of Prenanthes macrophylla Franch., along with 10 known compounds, 4-hydroxyphenylacetic acid (2), trans-ethyl caffeate (3), cis-ethyl caffeate (4), protocatechualdehyde (5), luteolin (6), luteolin-7-O-β-d-glucoside (7), 15-hydroxy-2-oxo-guai-3-en-1α,5α,6β,7α,10α,11βH-12,6-olide (8), 15-glucopyranosyloxy-2-oxo-guaia-3,11(13)-dien-1α,5α,6β,7α,10αH-12,6-olide (9), ursolic acid (10), and oleanolic acid (11). Their structures were elucidated on the basis of spectroscopic analyses including HR-ESI-MS, ESI-MS, (1)H and (13)C NMR, HSQC, HMBC, and ROESY, and chemical evidences.