Results on the optimization of analytical methods for the determination of phosphorus in phosphino-polycarboxylate (PPCA), used frequently as scale inhibitor during oil production, by ICP-AES and ICP-MS are presented. Due to the complex matrix of production waters (brines) and their high concentration in inorganic phosphorus, the separation of organic phosphorus prior to its determination is necessary. In this work, minicolumns of silica immobilized C18 were used. Optimization of the separation step resulted in the following working conditions: (1) prewashing of the column with methanol (80% v/v); (2) use of a flow rate of 5 mL/min and 10 mL/min, respectively, for the preconditioning step and for percolation of the water sample; (3) final elution of organic phosphorus with 7 mL of buffer of H3BO3/NaOH (0.05 M, pH 9) with a flow rate of 1 mL/min. Sample detection limits (3s) for different combinations of nebulizers and spectrometric methods, based on 10 mL water aliquots, are: ICP-AES -Cross flow (47 mg/L) and Ultrasonic (18 mug/L); ICP-MS -Cross flow (1.2 mug/L), Cyclonic (0.7 mug/L) and Ultrasonic (0.5 mug/L). Typical recoveries of organic phosphorus are between 90 and 95% and the repeatability of the whole procedure is better than 10%. The developed methodology was applied successfully to samples from the oil-well NA 46, platform PNA 2, Campos basin, Brazil. Assessment of the PPCA inhibitor was possible at lower concentrations than achieved by current analytical methods, resulting in benefits such as reduced cost of chemicals, postponed oil production and lower environmental impacts.