Substantial research efforts were made to assess the effects of submerged macrophytes on water quality improvement, but information on the mechanism of submerged macrophytes relative to the exchange of phosphorus (P) at the sediment–water interface is very limited. To help fill the void, a popular species, Ceratophyllum demersum L. was chosen to address the effects and mechanisms of submerged macrophyte growth on the processes of P exchange across the sediment–water interface. In treatment mesocosms (planted), equilibrium phosphorus concentration (EPC0) value falls from 68.4 to 36.0 µg/L, with a mean value of 52.5 µg/L. Conversely, the distribution coefficient (Kd) value has a predominantly increasing trend. But they are both significantly higher than an unplanted control (p < 0.05). Also, in the planted mesocosm, maximum phosphate sorption capacity (Qmax) was significantly reduced (4,721–3,845 mg/kg), and most of the linear correlations between different forms of phosphorus and sediment P adsorption parameters were affected (p < 0.05). The EPC0 Percentage Saturation percentages (EPCsat) in planted groups were 325% higher than that in control (p < 0.05). We conclude that C. demersum could promote the release of P from sediments, and soluble reactive phosphorus concentration in overlying water is probably the driving force for P exchange at the sediment–water interface.