BACKGROUND Rosemary leaves have been widely employed in the food and pharmaceutical industry due to the presence of important compounds. However, during the extraction process, in addition to the target biomolecules [chlorophyll (Chl), and rosmarinic acid], other components (phenolic compounds) are also extracted. This work focuses on the development of a sequential and selective protocol for the extraction and concentration of Chl using an aqueous micellar two‐phase system, and extraction and purification of rosmarinic acid using an aqueous two‐phase system (ATPS). RESULTS Firstly, the extraction and purification of Chls were studied. The Chls rich‐extract obtained using the best conditions of aqueous solution of Triton X‐100 (5 wt%) and phosphate buffer (50 mmol L−1), 50 °C solid–liquid ratio was evaluated at 1:100 and 60 min (Chl a = 69.3 ± 1.9 mg 100 g−1; Chl b = 41.1 ± 1.2 mg 100 g−1 and total Chl = 110.5 ± 3.1 mg 100 g−1) were submitted to temperature above cloud point. The Chl b and total Chl were concentrated 3.1 and 1.7 times. Further, the extraction and purification of rosmarinic acid were investigated. Ethanol, methanol, and acetonitrile (80 wt%) at 50°C were investigated; and after extraction, the rosmarinic acid rich‐extract were add in the ATPS composed of organic solvent + tripotassium phosphate (K3PO4). The extraction efficiencies were observed in the top phase (100%) for all systems. The highest purification factor was found using the ATPS based on acetonitrile (50 wt%) + K3PO4 (20 wt%). CONCLUSIONS The sequential protocols to extract Chls and purify rosmarinic acid can be applied. © 2020 Society of Chemical Industry