The adsorption of Aspilia africana extract and subsequent corrosion inhibition of aluminium alloy AA3003 in hydrochloric acid solutions have been investigated using gravimetric and electrochemical techniques. Inhibition efficiency increased with extract concentration and temperature rise. Polarization studies revealed that the extract essentially inhibited the cathodic reaction. An adsorption mechanism involving physisorption and chemisorption of extract constituents at low and high temperatures, respectively, has been proposed from the trend of adsorption-free energies. Quantum chemical computations and molecular dynamics simulations described the individual contributions of some extract constituents to the observed inhibiting effect.