The applications of natural polymeric flocculants due to their green feature has been recently received much more attention. In this work, the combined usages of a cationic starch-based coagulant and polyaluminum chloride (PACl) were extensively evaluated for various addition sequences in the coagulation of both raw (surface water from the Jiuxiang River) and synthetic turbid water (two kaolin suspensions with different initial turbidities). Two typical cationic starch-based coagulants with different structures (St-G and St-E) were tried. In comparison to St-G, St-E and PACl used individually as well as St-G and St-E dosed after PACl, the combination of the starch-based coagulants fed before PACl showed higher turbidity removal efficiency, which featured not only less optimal doses of both inorganic and organic coagulants but also lower residual turbidity. On the basis of a detailed analysis of the particle size and its distribution in solution supernatants before and after coagulation by two starch-based coagulants and PACl, polymeric coagulants preferentially coagulate the small-sized colloids due to their distinct long-chain structures, but PACl preferentially coagulates the medium-sized ones. Thus, the medium-sized particles that were previously formed by the starch-based coagulants would be collectively and effectively removed by the subsequent addition of PACl. The addition sequence of the inorganic and organic coagulants in their combined usage is an important factor for improvement of the turbidity removal efficiency in practice.