A chemically modified electrode is constructed based on a coumestan derivative and multiwall carbon nanotubes modified carbon paste electrode (CMWCNT-CPE). The surface charge transfer rate constant, k s, and the charge transfer coefficient, α, for the electron transfer between coumestan and MWCNT-CPE were estimated. CMWCNT-CPE presents a highly catalytic activity for adrenaline (AD) electrooxidation. The results show that the peak potential of AD at the CMWCNT-CPE surface shifted by about 145 mV toward negative values compared with that at the MWCNT-CPE surface. Differential pulse voltammetry exhibited three linear ranges and a detection limit of 0.2 μM for AD. For a mixture containing AD, uric acid (UA), and tryptophan (Trp), three signals corresponding to the analytes could well separate them from each other. Moreover, CMWCNT-CPE was used to determine AD in an adrenaline injection solution and UA in a human urine sample with satisfactory results. To confirm the proposed method, the AD injection solution and the urine sample were spiked with different certain amounts of AD, UA, and Trp.