Arbuscular mycorrhizal fungi (AMF) form mutualistic associations with the roots of 80–90% of vascular plant species and may constitute up to 50% of the total soil microbial biomass. AMF have been considered to be a tool to enhance phytoremediation, as their mycelium create a widespread underground network that acts as a bridge between plant roots, soil and rhizosphere microorganisms. Abundant extramatrical hyphae extend the rhizosphere thus creating the hyphosphere, which significantly increases the area of a plant's access to nutrients and contaminants. The paper presents and evaluates the role and significance of AMF in phytoremediation of hydrocarbon contaminated sites. We focused on (1) an impact of hydrocarbons on arbuscular mycorrhizal symbiosis, (2) a potential of AMF to enhance phytoremediation, (3) determinants that influence effectiveness of hydrocarbon removal from contaminated soils. This knowledge may be useful for selection of proper plant and fungal symbionts and crucial to optimize environmental conditions for effective AMF-mediated phytoremediation. It has been concluded that three-component phytoremediation systems based on synergistic interactions between plant roots, AMF and hydrocarbon-degrading microorganisms demonstrated high effectiveness in dissipation of organic pollutants in soil.