In this work, solid surface room-temperature phosphorimetry (SSRTP) was used to develop ultra-trace and selective methods for determination of chrysene and pyrene in complex samples containing several other polycyclic aromatic hydrocarbons (PAHs). Both chrysene and pyrene were selected because they are classificated by the U.S. Environmental Protection Agency (EPA) as two out of the sixteen major pollutants, affecting public health and marine ecosystems. The selective capability of SSRTP was explored through the selective external heavy atom effect and the adjustment of pH of the analyte solution used to carry out the analyte to the cellulose substrate. Cellulose modification with the use of the surfactant sodium dodecyl sulphat (SDS) has also been evaluated as well as the use of synchronous scanning to improve its spectral resolution. Silver nitrate together with SDS was identified as selective phosphorescence inducer for chrysene in the presence of pyrene and other PAHs which are being studied (anthracene, benzo[a] pyrene, 1- hidroxipyrene, fluoranthene, phenanthrene, benzo[ghi] perylene and 1,2 benzoanthracene). On the other hand, pyrene was selectively determined with synchronous and conventional phosphorescence scanning in substrates treated with lead nitrate as a selective inducer and using analyte carrier solution with pH 12. This selectivity towards pyrene was achieved in the presence of all the other tested PAHs, including the 1- hidroxipyrene, even though they have quite similar molecular structures. A factorial design was applied in order to verify mutual interactions among factors of the different variables and to find the best experimental conditions. It has been emphasized in this study: (i) statistical experimental analysis (testing the significance of the factors using the analysis of variation, F-test and t-test), (ii) graphic method (Pareto´s chart) to the interpretation and evaluation of the interactions among all the variables and obtained results, the model was refined whenever necessary so exclude irrelevant variables. After choosing the best experimental condition, the performance characteristics were obtained validating the proposed method. Statistical tests were applied in order to compare results obtained using a standard reference material analysis (NIST SRM 1647d). The proposed method was also compared with a reference analytical technique (HPLC with fluorescence detection) and the results obtained are within 95% confidence level. Chrysene and pyrene absolute detection limits were found in the ng order. The quantification of the variation sources associated to the measurement (the measurement´s uncertainty) was estimated based on ISO GUM and Monte-Carlo simulation method. Selectivity tests for chrysene and pyrene, in presence of the other PAHs were also performed. The methods were applied to different types of samples (fish bilis and spirit drink from sugar cane) and the recoveries were 109 (+ -) 18% (chrysene) and 108 (+ -) 20% (pyrene) by SSRTP. These results are comparable to ones obtained by HPLCFluorescence: 104 (+ -) 13% (chrysene) and 102 (+ -) 15% (pyrene). Characterization, homogeny and stability studies in a biological matrix (fish bilis of the type Mugil liza) and the estimation of uncertainty of the analysed material were also done. The measurement uncertainty was found in ng order (in terms of the effective mass deposit in the cellulose substrate).