Molar excess enthalpies of four binary systems for 2,4-pentanedione + (methanol, + ethanol, + 1-propanol, and + 2-propanol) at T = (298.15, 313.15, and 328.15) K and p = (0.1 and 10.0) MPa were determined by a high-pressure flow-mixing isothermal microcalorimeter. The molar excess enthalpies increased with an increase in the temperature and the molecular size of alcohols and decreased slightly with an increase in pressure. The experimental data were correlated by the Redlich-Kister equation and three local composition models (Wilson, NRTL, and UNIQUAC).