2,3-Pentanedione, acetaldehyde, and acetone are by-products found downstream in the sugar manufacturing process. 2,3-Pentanedione has various food and industrial-related uses, making it a product of interest. It can be recovered using extractive distillation recovery processes, whereby chemicals of similar boiling points are separated. Vapor-liquid equilibrium (VLE) measurements were conducted isobarically for the systems 2,3-pentanedione + {acetaldehyde or acetone} at 100, 150, and 200 kPa. Measurements were undertaken using a moderate pressure recirculating VLE still, capable of withstanding pressures up to 350 kPa. The measured VLE data were regressed using the gamma-phi (gamma-phi) approach and the nonrandom two-liquid activity coefficient model, which displayed satisfactory representation of the system behavior. None of the binary systems exhibit azeotropic behavior. All the binary systems displayed a positive deviation from Raoult's law.