This study provides data on the characteristic levels, spatial patterns, sources, and risk of n-alkanes (AHs) [octane, n-C8, to tetracontane, n-C40] and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments from the Escravos River Basin (ERB), Nigeria. The n-alkane and PAH concentrations in sediments were quantified by chromatographic methods. The concentrations of AHs and PAHs in the ERB sediments varied from 95 to 3430 µg g-1 and from 0.75 to 213 µg g-1, respectively. Both the concentrations of AHs and PAHs in ERB sediments exceeded their respective guideline values. The carbon preference index and other AH markers provide evidence that the AHs in the ERB sediments originated from petroleum sources. Ecological risk assessment indicated that the ecological risk relating to an organism's contact with PAHs in the ERB sediments was high. The possible carcinogenic risk arising from human exposure with PAHs in surface sediments through accidental oral ingestion and skin contact exceeded the safe level of 10-6, indicating a considerable probable cancer risk for fishermen and other inhabitants of the ERB. PAH isomer ratios and multivariate statistics suggested that the PAHs in sediments from the ERB originated from gas flaring inputs, discharges from oil drilling platforms, diesel engines, ships, and speed boats, and combustion of wood and other biomass.