The aim of this work is to study the precipitation mechanism of the intermetallic phases present in duplex stainless steels (UNS S32205 and UNS S32750), as well as to find out the most suitable method for detecting and analyzing accurately these secondary phases, particularly Sigma-phase, Chi-phase, nitrides and carbides. The samples were characterized after a solution annealing at 1080oC followed by an isothermal treatment at 830oC from 1 min to 9 h, with the purpose of figuring out the mechanism of chi-phase nucleation and nitrides formation in relation with the sigma-phase. The study has two main objectives: 1) to find out the most suitable technique for the detection, identification and quantification of the secondary phases, obtaining the best results with the combination of field emission scanning electron microscopy (FESEM) and backscattered electron detector (BSE) in comparison with the optical microscopy (MO); 2) to study the influence of the chemical composition on the nucleation mechanism of the intermetallic phases. It has been concluded that molybdenum balance content in chi-phase related to sigma phase is close to two, consequently the kinetics of nucleation and growth of these phases is remarkably faster when this alloying element content in the steel is higher. Chromium nitrides and carbides were also observed to precipitate as a result of the heat treatments carried out to the specimen wherein chromium nitrides role is a favorable site for the nucleation of sigma and chi phases.