With the first ever synthesis of monoazidopentaerythritol trinitrate, a comparative study of the properties of all azidonitrate derivatives from pentaerythritol tetranitrate (PETN) to tetraazidopentaerythritol (TAPE) was possible. The azides were prepared by halogen azide exchange and the remaining alcohols were then converted into the organic nitrate esters using acetyl nitrate. The resulting compounds pentaerythritol tetranitrate (PETN), monoazidopentaerythritol mononitrate (MAPETN), diazidopentaerythritol dinitrate (DAPEDN), triazidopentaerythritol mononitrate (TAPEMN), tetraazidopentaerythritol (TAPE) were analyzed for their chemical (XRD, NMR, EA, IR) and energetic properties (DTA/DSC, impact and friction sensitivity) and presented for comparison. An interesting trend of decreasing melting points from PETN to the triazide was observed, with the monoazide found to meet the thermal requirements for a melt-castable explosive. The mechanical sensitivities were successfully explained by Hirshfeld analysis. The energetic properties were calculated with the EXPLO5 code and show a decreasing performance towards the highly sensitive tetraazido derivative. Furthermore, PETN was successfully initiated with its tetraazido derivative TAPE.