The role of two polyelectrodes, poly-L-glutamate and poly-L-aspartate, in the growth of calcium phosphate crystal phases, has been investigated at constant supersaturation. Both molecules are strong inhibitors of HAP growth when present in the solution phase but also act as hydroxyapatite and (octacalcium phosphate)like crystal nucleators when adsorbed on germanium surfaces. The structure of the polymers in solution is presented and various adsorption models are analyzed. A "train-loop" structure of these long, flexible chain polymers on the crystal surface is consistent with all the adsorption (experimental and theoretical), inhibition, and electrophoretic mobility results.