Nine xanthone derivatives (1–9) were isolated from the roots of Polygala azizsancarii, which is a narrow endemic species for the flora of Türkiye. Based on all of the evidence, the structures of 1–9 were established as two previously undescribed xanthone O‐glucosides, 3‐O‐β‐D‐glucopyranosyloxy‐1,6‐dihydroxy‐2,5,7‐trimethoxyxanthone (1), 3‐O‐β‐D‐glucopyranosyloxy‐1,6‐dihydroxy‐2,7‐dimethoxyxanthone (2), and seven previously described xanthones, 1,3,6‐trihydroxy‐2,5,7‐trimethoxyxanthone (3), 1,3,6‐trihydroxy‐2,7‐dimethoxyxanthone (4), 1,2,3,4,7‐pentamethoxyxanthone (5), 1,3‐dihydroxy‐2,5,6,7‐tetramethoxyxanthone (6), 1,3‐dihydroxy‐4,7‐dimethoxyxanthone (7), 1,7‐dihydroxy‐3‐methoxyxanthone (8), and 1,7‐dihydroxy‐2,3‐methylenedioxyxanthone (9). The structures of the compounds were determined by spectroscopic methods, including 1D‐NMR (1H‐NMR, 13C‐NMR, DEPT‐135), 2D‐NMR (COSY, NOESY, HSQC, HMBC, INADEQUATE), and HR‐MS. The solid‐state structures of 1–4, including the absolute configurations of the stereogenic carbons of the sugar moiety in 1 and 2, were established by X‐ray crystal‐structure analyses. For the newly described compounds, the trivial names sancarosides A (1) and B (2) are proposed.