Four caffeoylquinic acid (CQA) derivatives, 5‐O‐caffeoylquinic acid (1), 3,5‐di‐O‐caffeoylquinic acid (3), 4,5‐di‐O‐caffeoylquinic acid (4), and 3,4,5‐tri‐O‐caffeoylquinic acid (5), have been isolated from Artemisia herba‐alba growing wild in Algeria, using the on‐line HPLCDADDPPH radical‐scavenging detection technique as guidance. In the course of the purification work, the non‐frequent (E)‐2‐(β‐D‐glucopyranosyloxy)‐4‐methoxycinnamic acid (2) has also been isolated. The CQAs showed fair‐to‐good antioxidant activities determined by the DPPH. scavenging assay. The structures of the five isolated compounds were determined by spectroscopic methods. The on‐line HPLCDADDPPH technique allowed for a rapid pinpointing of antioxidants in the studied plant, accomplishing the facile guided isolation of the target molecules. Algerian A. herba‐alba could be an interesting source of natural antioxidants that deserve further work.