Baccharis is one of the largest genera of Asteraceae and its species are used in folk medicine for several medicinal purposes due to the presence of bioactive compounds. We investigated the phytochemical composition of polar extracts of B. sphenophylla. Using chromatographic procedures, diterpenoids (ent-kaurenoic acid), flavonoids (hispidulin, eupafolin, isoquercitrin, quercitrin, biorobin, rutin, and vicenin-2), caffeic acid, and chlorogenic acid derivatives (5-O-caffeoylquinic acid and its methyl ester, 3,4-di-O-caffeoylquinic acid, 4,5-di-O-caffeoylquinic acid, and 3,5-di-O-caffeoylquinic acid and its methyl ester) were isolated from polar fractions and are described. The extract, polar fractions, and fifteen isolated compounds were evaluated in relation to radical scavenging activity using two assays. Chlorogenic acid derivatives and flavonols exhibited higher antioxidant effects, confirming that B. sphenophylla is an important source of phenolic compounds with antiradical properties.