Extracts from several plants of the family Bignoniaceae from Panama were submitted to a rapid DPPH TLC test for the detection of radical-scavenging activity. The MeOH extract of the stems of Jacaranda caucana, a tree that grows from Costa Rica to Colombia, was selected due to its interesting activity and the lack of phytochemical studies on the polar extract. This extract was partitioned between ethyl acetate, butanol, and water. The EtOAc fraction afforded two new phenylethanoid glycosides (1, 2), along with protocatechuic acid, acteoside, and jionoside D. Further purifications yielded isoacteoside and martynoside. The BuOH fraction afforded a new rhamnosyl derivative of sisymbrifolin (8), a neolignan. The structures were determined by means of spectrometric methods, including 1D and 2D NMR experiments and MS analysis.