Pimpinella candolleana is known as Miao ethnic herbal medicine in Guizhou for the treatment of icteric hepatitis, acute cholecystitis and other diseases. To investigate the chemical constituents of P. candolleana and their anti-inflammatory activities, the chemical constituents from the 70% ethanol extract of P. candolleana were separated by silica gel, Sephadex LH-20, Toyopearl HW-40F, Toyopearl HW-40C, ODS and other column chromatography technologies, and their structures were elucidated by extensive spectroscopic analysis such as nuclear magnetic resonance (NMR) and mass spectrum (MS). The inflammatory cell model, built by LPS-induced RAW264.7 macrophage cells, was used to evaluate the anti-inflammatory activity. The results were as follows: (1) Twenty compounds from P. candolleana were isolated and identified of including vanillin (1), sesamin (2), 2-methyl-2-hydroxy-5-methoxy berz (d) hydrofuran-3-one (3), procatechin (4), 1,5-dihydroxy-2,3-dimethoxyxanthone (5), isorhamnetin (6), kaempferol (7), 8-hydroxy-2-methylchromone (8), luteolin (9), quercetin (10), 1-O-β-D-glucopyranosyl-(2S,3S,4R,8E)-2-[(2′R)-2′-hydroxypalmitoylamino]-8-octadecene-1,3,4-triol (11), isorhamnetin-3-O-β-D-galactopyranoside (12), isoquercitrin (13), norswertianolin (14), luteolin-6-C-α-L-arabinoside (15), kaempferol-3-O-β-D-galactopyranoside (16), kaempferol-7-O-β-D-glucopyranoside (17), luteolin-7-O-β-D-glucopyranoside (18), isovitexin (19), rutin (20). Compounds 1, 3, 4, 6, 7, 10, 13, 16, 18, and 20 were obtained from this plant for the first time. (2) The anti-inflammatory results showed that compounds 2-10, 12, 18 and 19 could significantly inhibit the LPS-induced NO content in RAW264.7 cells (P