An improved solvent bar microextraction (SBME) combined with HPLC was applied to rapidly determine oleanolic acid (OA) and ursolic acid (UA) in Chinese medicinal herbs (CMHs), and to investigate drug–protein binding. Variables influencing SBME were investigated and optimized. Under optimal conditions, the linear ranges of 3.6–1,820 ng mL−1 for OA and 4.2–2,080 ng mL−1 for UA were obtained with square correlation coefficients of 0.9996 and 0.9997, respectively. The detection limits were 1.3 ng mL−1 for OA and 1.5 ng mL−1 for UA. The relative standard deviations were lower than 9.4 %. The protein-binding rates, the numbers of binding sites, and the binding constants of OA and UA were also obtained via the method. It has been demonstrated that SBME can not only be a simple, rapid and efficient sample preparation method for determination of active components from CMHs but also be a potential research protocol for protein-binding interactions.