Chlorite and serpentine are common magnesium-containing gangue minerals in copper sulfide flotation. In this study, sodium alginate, a natural hydrophilic polysaccharide, was introduced as a selective depressant for these gangue minerals. Micro-flotation tests were conducted on both single minerals and synthetic mixtures. The flotation results showed that sodium alginate could simultaneously depress the flotation of chlorite and serpentine effectively, but seldom influenced the floatability of chalcopyrite at pH 9. In the ternary mixture flotation, a concentrate with a Cu grade of 31% could be achieved at Cu recovery of 90%. The selective depression of chlorite and serpentine was also validated by the real ore flotation experiments. The selective depression mechanism was investigated through adsorption tests, zeta potential measurements, and FTIR analyses. The adsorption density results implied that sodium alginate selectively adsorbed on the surface of phyllosilicates, but no adsorption on the chalcopyrite surface was observed. The zeta potential results showed that the sodium alginate could selectively decrease the surface charge of chlorite and serpentine. The FTIR results revealed the chemical adsorption of sodium alginate on the chlorite and serpentine surface and no form of adsorption on chalcopyrite, agreeing well with the adsorption density results. On the basis of these results, a selective adsorption model of sodium alginate on the mineral surface was proposed.