The concentrations of arsenic in oil can vary of 10 the 30 mgkg-1. The selenium is found in effluent of the petroliferous industry, had its presence in the oil, between 0.03 -1,4 mg.L-1 depending on its geochemistry origin. For chemical reasons, arsenic shows a high affinity to sulfur, similar as selenium, thus following this element through the whole petroleum refining process, reaching the sour water strippers, where separation of sulfur from other inorganic species takes place. In this phase of the refining process, when it can occur the most severe corrosions, these ametais remain, probably, immobilized in the deep one of the towers being able to be carry out the Water Unit Treatment. Before launched to the environment, these waters must be treated aiming at its adequacy Brazilian Legislation (CONAMA, Res. 357/05). The elimination efficiency depends on the employed process and directly is related to the species gifts in these waters. The Ions Chromatography (CI) coupled to the ICP-MS was the choice for the development of this work - speciation of arsenic and selenium in stream watery of refining process. A good chromatographic resolution was reached using column of ionic exchange and NaOH (0,1mol.L- 1) as mobile phase and cell suppressor for the minimizes the signal from the background and a possible deposition lens and coins in ICPMS. The reached Limits of Detention for the species of arsenic had been 0,15 and 0,18 (mi)g.L-1 for As (III) and As (V), respectively. The Limits of Detention for the species of selenium had been of 0,04, 0,05 and 0,05 (mi)g.L-1 Se (IV), Se (VI) and SeCN, respectively, these established results using a loop of 100 (mi)L. The total content of the studied elements determined by two analytical techniques, ICPMS and GFAAS and the chromatographic recovery calculated by both results. The developed method was tested in three certified reference materials, BCR 713, 714 and 715, having been gotten an agreement with the certified values. Finally, the methodology was applied in the samples of different stages of the process of two oil refineries. All samples proceeding from effluent were below oft he limit established for the Brazilian Legislation. The methodology proposal revealed adequate for accomplishment, monitoring an speciation for arsenic and selenium in complex matrices, as existing in the stages of Fluid Catalytic Cracking and the Units of Treatment of Residual Water, as well as in an environmental samples.