High purity nitrate esters of the pentaerythritols can be successfully synthesized from correspondingly high purity reagents. The latter are not commercially available, but may be purified through molecular distillation and/or fractional crystallization from xylene. The isolated products are ultimately saponified to reagents of high purity. The nitration of high purity pentaerythritols using 97-100% nitric acid proceeds smoothly resulting in yields of the corresponding nitrate esters which are nearly quantitative. Thin layer chromatography (TLC) indicates numerous satellite impurities present in all the pentaerythritol-tetranitrate (PETN) homologs with the exception of ultrapure PETN itself. Separation and isolation of these contaminants, from a high impurity concentrate, was achieved by liquid chromatography. IR spectra of these components suggests these compounds are the various homologs and pentaerythryl ethers with a mixture of hydroxyl and nitrate functional groups.