In this experimental study, a production grade engine was modified to operate in two combustion modes, namely conventional diesel combustion (CDC) and premixed charge compression ignition (PCCI) combustion, depending on the engine load. For mode switching, an open electronic control unit was programmed to operate the engine in PCCI combustion mode up to medium engine loads and then automatically switching it to CDC mode at higher engine loads, by varying the fuel injection parameters and the exhaust gas recirculation rate. For performance and emission characterization in the entire load range (idling-to-full load) of the test engine, a test cycle of 300 s was used, which included CDC mode, PCCI combustion mode, and transition between these two modes. Results showed that both mineral diesel and B20 (20% biodiesel blended with mineral diesel, v/v) fueled PCCI combustion resulted in significantly lower NOx and particulate emissions compared to baseline CDC. Relatively lower exhaust gas temperature in PCCI combustion mode led to slightly inferior engine performance and higher concentration of unregulated emission species such as SO2, HCHO, and so on. B20-fueled engine resulted in relatively lower unregulated emission species and particulates compared to the mineral diesel–fueled engine in both the combustion modes. In CDC mode, contributions of accumulation mode particles were significantly higher compared to nucleation mode particles. Relatively lower emission of aromatic compounds in PCCI combustion mode compared to CDC mode was another important finding of this study; however, B20-fueled engines resulted in slightly higher emissions of aromatic compounds.