The relative roles of surface acidity and hydrophobicity in the methylation of fatty acids (C(8) - C(18)) to the corresponding methyl esters were investigated over three solid acid catalysts: Fe-Zn double-metal cyanide (DMC), sulfated zirconia (SZ), and Al-MCM-41. The esterification reaction was faster and the apparent activation energy was lower over SZ and Al-MCM-41 than on DMC because of their higher acid strength, specific surface area, and pore diameter. Over SZ and Al-MCM-41, the apparent activation energy for esterification increased with the chain length of the fatty acid. A reverse trend, however, was observed over DMC. The relative adsorption of methanol and fatty acids (compared to water) was higher on DMC than on SZ and Al-MCM-41. Hence, in addition to the acidic and textural properties, surface hydrophobicity and relative surface coverage by reactants/products also play an important role in reactions of long-chain fatty acids with alcohols on solid catalysts.