Prostate cancer has an increasing incidence and there is an urgent need for development of new serum biomarkers for early diagnostic as the ones known are ineffective. The aim of the study was to use untargeted metabolomics in order to identify and characterize small metabolite fingerprints in patients with normal vs pathologic values of PSA ( previously determined by electrochemiluminiscence).A cohort of one hundred patients with different Prostate Specific amtigen values were investigated by untargeted metabolomics. The serum small metabolite profile determined by high performance liquid chromatography coupled with mass spectrometry, LC-QTOF(ESI + )MS in order to identify specific biomarkers, for normal patient group (PSA = 0-4 ng.ml) and four pathologic groups, having PSA values from 4 to >1000 ng/ml.The major molecules identified in the samples were polar phospholipids, maily lysophosphatidyl choline derivatives, having m/z values from 496 to 524, like LPC(O-16:0/O-1:0), LPC(18:1/2:0) or PS(18:1(9Z)/0:0), LPC(18:2(9Z,12Z)/0:0 and their isomers and LPC(O-18:1(11Z)/2:0), respectively. Also, small molecules (free fatty acids and prostaglandin derivatives) were identified and are significantly different in pathologic vs normal serum samples. Generally the pathologic samples had increased concentrations of all above mentioned molecules. The Principal Component analysis showed , by plot and loadings scores, significant clustering of normal vs pathological groups.