A HPLC procedure has been optimized and successfully applied to porphyrins of environmental interest, such as etio and octaethylporphyrins and their VO and Ni compounds. The use of UV-Vis diode array allowed the detection of the analytes within the 5-15 ng/ml range. In order to achieve greater specificity and some structural information, the coupling of liquid chromatography with mass spectrometry was investigated, and the particle beam interface conditions were optimized. Electron impact (EI) spectra, comparable to those reported in the literature were obtained. The entire procedure has been applied to a real marine sediment, previously spiked with porphyrins to resemble oil-contaminated samples. The results pointed out that the method is suitable for such levels of analytes (5-10 microg/ml), allowing their identification and quantification with no need for purification steps.