Environmental pollution caused by lead and vanadium is almost entirely due to industrial activities, such as the production of steel, pigments, photographic materials and insecticides. The concentration and chemical speciation of Pb and V were studied in surface sediments from 11 stations off Nile River Delta. Sequential extraction technique was applied to assess the four (exchangeable, acid-reducible, oxidizable-organic and residual) fractions in surface sediment, also to obtain an overall classification of lead and vanadium pollution in this area through its spatial distribution. This investigation was the first study on the basis of the chemical speciation of Pb and V in surface sediments off Nile Delta. The total concentrations of metals were ranged (22.8–41.3 μg g−1) for Pb and (66.6–142.5 μg g−1) for V. The chemical speciation in most sampling stations was in the order of Residual > acid-reducible > oxidizable-organic > exchangeable for Pb and in the order of Residual > oxidizable-organic > exchangeable > acid-reducible for V. The results showed that the Pb in surface sediments off Nile River Delta existed in the nonresistant fractions while vanadium existed in the resistant fractions. The degree of surface sediments contamination was determined for individual contamination factors (ICF) and global contamination factor (GCF). The result of ICF and GCF values showed that those stations located in the vicinity of municipal area (especially Lake Burullus outlet) had high potential risk to fauna and flora of study area. Risk assessment code (RAC) analysis indicated that although Pb presented a moderate overall risk to the aquatic environment, vanadium showed a low risk (RAC < 10%) at six sites.