Polysaccharide biopolymers are biomacromolecules derived from renewable resources with versatile functions including thickening, crosslinking, adsorption, etc. Possessing high efficiency and low cost, they have brought wide applications in all phases of petroleum recovery, from well drilling to wastewater treatment. The biopolymers are generally utilized as additives of fluids or plugging agents, to correct the fluid properties that affect the performance and cost of petroleum recovery. This review focuses on both the characteristics of biopolymers and their utilization in the petroleum recovery process. Research on the synthesis and characterization of polymers, as well as controlling their structures through modification, aims to develop novel recipes of biopolymer treatment with new application realms. The influences of biopolymer in many petroleum recovery cases were also evaluated to permit establishing the correlations between their physicochemical properties and performances. As their performance is heavily affected by the local environment, screening and testing polymers under controlled conditions is the necessary step to guarantee the efficiency and safety of biopolymer treatments.