The on-board distillation system (OBDS) was developed to extract, from gasoline, a high-volatility fuel for exclusive use during the starting and warm-up periods. The use of OBDS distillate fuel results in much improved mixture preparation, allowing combinations of air/fuel ratio and ignition timing that are not possible with gasoline, even with a fully warm engine. The volatility of the distillate is a function of the parent fuel volatility; however, the variability in distillate quality can be diminished via manipulation of the OBDS operating conditions. Thus, it is possible to develop aggressive starting calibrations that are relatively immune to variations in pump gasoline volatility. The key benefits provided bythe OBDS fuel relative to standard gasoline were found to be (1) improved mixture preparation allowing a 70% reduction of cranking fuel requirements, elimination of air-fuel mixture enrichment during the warm-up period, and significant extension of warm-up ignition timing retard; (2) a 57% decrease in catalyst light-off time, (3) emissions reductions over the FTP drive cycle of 81% for regulated hydrocarbons (NMOG); (4) emissions index (NMOG) approaching that of SULEV/PZEV vehicles; and (5) an apparent 1% increase in fuel economy over the FTP drive cycle.