Pilloin was synthesized by methylation of luteolin and its structure was characterized by element analysis, H-1-NMR, IR, and single-crystal X-ray diffraction analysis. It crystallizes in the monoclinic crystal system, space group P2(1)/n, with a = 7.336(3) angstrom, b = 14.257(5) angstrom, c = 13.298(5) angstrom, beta = 93.516(5)degrees. The flavone molecules of pilloin are linked into puckering sheets via R-3(3) (14) and R-2(2)(g) graph- set ring motifs defined by the C-H... 0 and O-H...O hydrogen bonds. pi-pi stacking interactions lead to the flavone skeletons of columns that are held together through centrosymmetric R-2(2) (8) motifs. Hydrogen bonding and aromatic pi - pi stacking interactions assemble the title compound into a 3-dimensional network structure.