Polypyrrole-modified iron oxide nanomaterials have been synthesized employing a one-step hydrothermal protocol. The influence of the reaction temperature has been investigated by performing the synthesis at four different temperatures (Ppy@Fe 2 O 3 -120 °C, Ppy@Fe 2 O 3 -140 °C, Ppy@Fe 2 O 3 -160 °C, and Ppy@Fe 2 O 3 -180 °C). Synthesized materials exhibited an unprecedentedly peculiar morphology (star/coral reef-like architectures), induced by the presence of pyrrole in the reaction media. Full characterization of the samples revealed the critical influence of temperature on the crystallinity, textural properties and specially on (C+N)/Fe surface ratios in the materials. As-synthesized nanohybrids were integrated into electrodes to construct supercapacitor devices. A effective tuning of the electrochemical features was achieved by controlling the (C+N)/Fe ratio on the surface, strongly dependent on reaction temperature. The best electrochemical performance was reached by Ppy@Fe 2 O 3 -180 °C nanohybrid, which exhibited a remarkable capacitance value of 560 F g -1 at a current density of 5 A g -1 and an outstanding cycling stability of ca. 97.3% after 20 000 cycles of charge-discharge at 40A g -1 was reached. © 2019 American Chemical Society.