This paper shows one of the few examples in the literature on the feasibility of novel materials from natural and biocompatible polymers like inulin (INU) or glycol chitosan (GCS) templated by the formation of o/w (inverse) high internal phase emulsion (HIPE). To the best of our knowledge, this is the first example of inverse polyHIPEs obtained from glycol chitosan or inulin. The obtained polyHIPEs were specifically designed for possible wound dressing applications. The HIPE (pre-crosslinking emulsion) was obtained as inverse HIPE, i.e., by forming a cream-like 80:20 v/v o/w emulsion by using the isopropyl myristate in its oil phase, which is obtained from natural sources like palm oil or coconut oil. The surfactant amount was critical in obtaining the inverse HIPE and the pluronic F127 was effective in stabilizing the emulsion comprising up to 80% v/v as internal phase. The obtained inverse HIPEs were crosslinked by UV irradiation for methacrylated INU or by glutaraldehyde-crosslinking for GCS. In both cases, inverse poly-HIPEs were obtained, which were physicochemically characterized. This paper introduces a new concept in using hydrophilic, natural polymers for the formation of inverse poly-HIPEs.