This study aims to investigate the chemical consituents from Polygonatum kingianum. The ethanol extract from the rhizomes of P. kingianum were isolated and purified by silica gel, ODS, Sephadex LH-20 column chromatography and semi-preparative HPLC. The structures of isolated compounds were elucidated by spectral techniques and comparison with literature data. Fourteen compounds were obtained and identified as (25S) -kingianoside Z₁ (1), (25R)-kingianoside G (2), sarsasapogenin (3), smilagenin (4), 20-hydroxyecdysone-2-acetate (5), 20-hydroxyecdysone (6), polygonatone H (7), 4′,5,7-trihydroxy-6,8-dimethylhomoisoflavanone (8), disporopsin (9), 5,7-dihydroxy-6-methyl-3-(2′,4′-dihydroxybenzyl)-chroman-4-one (10), neoliquiritin (11), 4′-demethylleucomin-7-O-β-D-glucopyranoside (12), isoliquiritigenin (13), (+)-syringaresinol (14). It should be pointed out that compound 1 is a new isospirostanol saponin，and compounds 4, 5, 6, 7, 8, 10, 12, 14 were obtained from the Polygonatum kingianum for the first time.