The present investigation describes the synthesis of capsules with a poly(pyrrole‐phenosafranin) cross‐linked shell. The capsules are prepared in a water solution by the facile single‐step chemical oxidative polymerization of monomers within hydrophobic interior of lipid bilayers that act as temporary scaffolds created by liposomes from 1,2‐dilauroyl‐sn‐glycero‐3‐phosphatidylcholine. The polypyrrole links phenosafranin units via amino groups, thus new thermostable nanocapsules are obtained without additional cross‐linking agents. Their spherical shape is confirmed by electron microscopy. Wide spectral characteristics of capsules by using different analytical methods provide detailed information about their structures.