Novolak resins fractionated using a liquid/liquid centrifugal fractionation/separation technique were characterized and contrasted to resins fractionated by conventional methods. The new fractionation method resulted in higher yields of resins with comparable or improved functional properties when used in i-line sensitive (365 nm) photoresist formulations. By characterizing the isolated resin and the lower molecular weight (Mw) fractions removed during fractionation, a better understanding of the structural differences associated with the fractionation processes could be determined. The potential for improving the fractionation/separation process and for obtaining higher yields and more consistent resists with the resins was identified.