A highly sensitive flow analysis system has been developed for the trace determination of reactive phosphate in natural waters, which uses a polymer inclusion membrane (PIM) with Aliquat 336 as the carrier for on-line analyte separation and preconcentration. The system operates under flow injection (FI) and continuous flow (CF) conditions. Under optimal FI conditions the system is characterised by a linear concentration range between 0.5 and 1000 μg L(-1)P, a sampling rate of 10h(-1), a limit of detection of 0.5 μgL(-1)P and RSDs of 3.2% (n = 10, 100 μg L(-1)) and 7.7% (n = 10, 10 μg L(-1)). Under CF conditions with 10 min stop-flow time and sample solution flow rate of 1.32 mL min(-1) the flow system offers a limit of detection of 0.04 μg L(-1)P, a sampling rate of 5h(-1) and an RSD of 3.4% (n=5, 2.0 μg L(-1)). Interference studies revealed that anions commonly found in natural waters did not interfere when in excess of at least one order of magnitude. The flow system, operating under CF conditions, was successfully applied to the analysis of natural water samples containing concentrations of phosphate in the low μg L(-1)P range, using the multipoint standard addition method.