To investigate the chemical constituents in the stems of Chirita longgangensis var. hongyao, methanol extract of the stems was subjected to column chromatography with various chromatographic techniques. One new beta-naphthalenecarboxylic acid biglycoside, 1, 4-dihydroxy-2-naphthalenecarboxylic acid methyl ester-4-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (1) was isolated, along with two known compounds: isotaxiresinol 4-O-methyl ether (2) and (R)-7-hydroxy-alpha-dunnione (3). Compound 2 was first obtained from Chirita genus and compound 3 was isolated from this plant for the first time. All structures were elucidated on the basis of spectral and chemical evidence, and the NMR spectroscopic data of compound 2 was published for the first time.