A five-step sequential extraction technique, following Tessier's protocol, has been applied to determine the chemical association of Cd, Cu, Fe, Pb, and Zn with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in surface sediments from 14 stations off the Libyan Mediterranean coast. This study is a first approach of chemical fractionation of these metals in one of the most economically important area of the Libyan coastline in Mediterranean Sea. The total metal content was also determined. The total concentration of metals ranged from 5-10.5 mg/kg for Cd, 9.1-22.7 mg/kg for Cu, 141.8-1056.8 mg/kg for Fe, 18.9-56.9 mg/kg for Pb, and 11.6-30.5 mg/kg for Zn. The results of the partitioning study showed that the residual form was the dominant fraction of the selected metals among most of the studied locations. The degree of surface sediment contamination was computed for risk assessment code (RAC), individual contamination factor (ICF), and Global contamination factor (GCF). Risk assessment code classification showed that the relative amounts of easily dissolved phase of trace metals in the sediments are in the order of Pb>Zn>Cd>Cu>Fe. The results of ICF and GCF showed that Sirt and Abu Kammashand had higher GCF than other sites indicating higher environmental risk. In terms of ICF value, a decrease order in environmental risk by trace metals was Pb>Zn>Cu>Cd>Fe. Therefore, Pb had highest risk to water body.