Brain study methods mainly rely on neurochemical detection and electrophysiology, respectively studying the molecular dynamics and electrical activity in the brain cellular environment. The combined and simultaneous use of both study modes holds great promises for patients and researchers, in line with the treatment research but rely on multifunctional platforms (materials, devices, techniques...) still to be developed. Here, we present a new macro-porous composite material made up of PEDOT and carbon nanofibers (CNFs), coated on a flexible neural microelectrode array. A fully controlled one-shot electrodeposition strategy was developed to coat flexible Au-microelectrode surfaces with macro-porous CNF/PEDOT nanocomposite. The oxidized CNFs were used as a dopant and infused within the conductive PEDOT, electrochemically, in such a way that their excellent electronic, mechanical, chemical properties, and resulting combined performances can be exploited to yield better quality neural recordings, electrical stimulation and neurotransmitter detection.