The present contribution screens the specific activity of various inorganic and enzymatic based materials in the esterification of oleic acid that is typically used as a test reaction for the production of biodiesel from high free fatty acid feedstocks. The inorganic materials investigated in this contribution are bulk fosfotungstic heteropoly acid of the Wells Dawson structure H6P2W18O62.nH(2)O (HPA), as well as dispersed on titanium dioxide 18 % w/w H6P2W18O62/TiO2 and the insoluble cesium salt of the Wells Dawson heteropoly anion Cs2H4P2W18O62. Additionally, the commercial biocatalyst NovozymA (R) 435 (immobilized lipase B of Candida antarctica) and a self-supported lipase of vegetable origin obtained from the latex Araujia sericifera (ASL) were studied among the materials of enzymatic nature. The density and accessibility of Bronsted acid sites have a key role in the specific activity of the fosfotungstic based heteropoly compounds. The HPA dispersed over an oxide support catalyzed the esterification of the fatty acid in a heterogeneous fashion with the highest activity (6.4 A mu mol mg(-1) h(-1) at 85 A degrees C) among the inorganic materials. In contrast, the enzymatic materials are more active at lower temperature than the inorganic ones. Particularly, ASL catalyzed the homogenous methanolysis with the highest specific activity (30.7 A mu mol mg(-1) h(-1) at 40 A degrees C) at the lowest temperature among the materials assayed.