From the ethyl acetate extract of the aerial parts of Baeckea frutescens, a new flavonoid, 6,8-di-C-methylkaempferol (1), and three new flavonoid glycosides, 6,8-di-C-methylkaempferol 3-O-α-L-rhamnopyranoside (2), 6-C-methylquercetin 3-O-α-L-rhamnopyranoside (3), and 6-C-methylquercetin 4′-O-β-D-glucopyranoside (4), along with four known flavonoids were isolated. Their structures were elucidated by extensive spectroscopic methods including 1D and 2D NMR experiments, as well as ESI-MS analysis. All the new compounds were tested for their antioxidant activity in the 1,1-diphenyl-2-pecrylhydrazyl (DPPH) radical scavenging assay system. Compounds 3 and 4 showed potent activity with IC50 values of 12.1 ± 0.5 and 13.5 ± 0.9 (μM), respectively.