The calcite shields produced by unicellular marine algae demonstrate the remarkable crystal control that organisms can achieve through biomineralization. Emiliania huxleyi produces complex polysaccharides ("coccolith associated polysaccharides", CAP) that regulate crystal morphology by preferentially attaching to calcite acute step edges, thus promoting growth of the specific crystal faces required for design of that species of coccolith. However, to control crystal growth, the alga must be able to control CAP behavior at the local scale, so its functionality can be switched on and off. Here, we show that the functionality of CAP from E. huxleyi depends directly on solution composition. We used atomic force microscopy (AFM) to investigate the behavior of calcite surfaces under varying pH, in the presence of CAP and cations chosen to test the role of ionic potential, that is, charge per unit radius (K + , Na + , Sr 2+ , Ca 2+ , Mg 2+ , Zn 2+ , and Eu 3+ at 1 M charge concentration). Site-specific adsorption to calcite steps, essential for regulating morphology, only occurs in neutral to acidic pH (range investigated: 3.4-7.7) and in the presence of K + , Na + , Sr 2+ , and Ca 2+ . Basic pH (range investigated: 9.9-11.3), or cations of higher ionic potential than Ca (Mg 2+ , Zn 2+ , and Eu 3+ ), caused CAP to ignore step edges, turning off its normal functionality. We propose that complexation between cations, CAP, and the calcite surface controls CAP behavior. Thus, cations provide an on/off switch for CAP function, with the power to regulate and disturb coccolith biomineralization as well as to control calcite growth at the unblocked precipitation sites.