The direct determination of P in biodiesel by high-resolution continuum source graphite furnace atomic absorption spectrometry has been investigated. A slow drying stage proved to be essential for good repeatability. Optimization was performed by a D optimal planning. The atomization temperature and modifier composition were the most relevant parameters. Thus, using a mixture of Pd (30 μg) and Mg(NO3)2 (20 μg) as the modifier, previously deposited onto the platform of the graphite tube and dried, a five step drying stage, and pyrolysis and atomization temperatures of 1000 and 2700 °C, respectively, a limit of detection of 0.5 μg g− 1 was obtained. The analysis of biodiesel of different origins confirmed that external calibration with organic P standard solutions, diluted in P-free biodiesel, could be used. In this way, excellent agreement between the found and expected results was observed in the analysis of an ANP interlaboratorial exercise sample.