The surface species present on silica/alumina-supported sodium phosphates, active catalysts for the conversion of lactic acid to acrylic acid and 2,3-pentanedione, are examined by pre- and postreaction MAS P-31-NMR and FTIR spectroscopies, Species present following lactic acid conversion are identified by transmission FTIR of phosphates supported on silicon disks (as a model catalyst system) and verified by P-31-NMR and diffuse reflectance IR spectroscopy of actual catalysts used in reaction. Monosodium phosphate (NaH2PO4) condenses to a mixture of sodium polyphosphate (NaPO3)(n) and sodium trimetaphosphate (Na3P3O9), which exhibit little catalytic activity for converting lactic acid to desired products. Disodium phosphate (Na2HPO4) condenses to tetrasodium pyrophosphate (Na4P2O7), and proton transfer from lactic acid to pyrophosphate results in the formation of sodium lactate. Trisodium phosphate (Na3PO4) accepts a proton from lactic acid to form sodium lactate and disodium phosphate, which condenses to pyrophosphate. The presence of pyrophosphate and sodium lactate on supported disodium and trisodium phosphates explains their similar catalytic properties; the larger quantity of sodium lactate present on trisodium phosphate leads to higher conversions at lower temperatures.