The effect of sodium sulfite (Na2SO3) on the flotation behaviour of bornite and tennantite is reported in this work. Flotation tests were performed using pure minerals of bornite and tennantite under various concentrations of sodium sulfite at pH 9. The flotation results indicated that sodium sulfite exhibited a depressing effect on the floatability of bornite in the presence of 0.1 mM PAX. However, tennantite remained floatable after the addition of sodium sulfite in the presence of 0.1 mM PAX. The flotation tests using mixed bornite and tennantite confirmed the flotation results of single minerals. Surface characterisation using X-ray photoelectron spectroscopy (XPS) was performed to explain the flotation results. A mechanism is proposed based on the XPS analysis results.