The extent of environmental contamination and sources of polycyclic aromatic hydrocarbons (PAHs) compounds to sediments of the Niger Delta, Nigeria were assessed using combined chemical analysis and toxicity bioassay techniques. Concentrations of two- to six-ring PAHs of molecular mass 128-278 and toxicity to Vibrio fischeri and Lemna minor are considered in this investigation. Levels of the sum of the 16 USEPA priority pollutant PAHs varied from 20.7 to 72.1 ng/g dry weight. Sediment PAH levels were highest in samples collected from Delta Steel located at the outskirts of Warri, and Quality control centre, Ughelli West; with total PAH concentrations of 72.1 and 67.5 ng/g dry weight, respectively. The overall levels of PAHs in this study are low compared to other regions and reveal moderate PAHs pollution in the sediments of the Niger Delta. Two- and three-ring aromatic hydrocarbons predominated in almost all the sediments, which indicate a petrogenic origin. The sediment total PAH (PAHtot) concentration, normalized to organic carbon content (OC), ranged from 120.2 to 1.99 ng PAHtot/mg OC; and showed distinctively that the sedimentary organic matter of the sample from Delta Steel is highly contaminated with PAHs, and had a value of 120.2 ng PAHtot/mg OC. The toxicity bioassays indicated that the sample collected from Warri Refinery Area (SDWRR) was the most toxic to V. fischeri, with an EC50 value of 0.45 mg sediment equiv./mL test medium; and samples from Ogunu (SDOGN) and Warri Refinery area (SDWRR) showed high toxicity to L. minor, with percent inhibitions of 42.6% and 33.67%, respectively, after 7 days of exposure. The total PAH concentrations showed no correlation with toxicity bioassays, and thereby implied that chemical analysis of PAHs cannot be an indicator of sediment toxicity.