A clear need exists for novel nanostructured materials that are capable to meet the performance criteria of a number of neuronal therapies including neural recording, stimulation and sensing of bioactive molecules at the electrode-tissue interface. By combining Poly (3,4-ethylenedioxythiophene) (PEDOT), with Carbon Nanofibers (CNFs), we demonstrate a versatile approach for the synthesis of a novel composite material PEDOT:CNF with remarkable electrochemical properties, combining low impedance, high surface area, high charge injection capability and reliable neurotransmitters monitoring using amperometric techniques. The oxidized CNFs were utilized as dopants of PEDOT to prepare the composite coatings through electrochemical deposition on neural microelectrodes arrays (MEA). The PEDOT:CNF modified microelectrodes demonstrated the low specific impedance of 1.28 MΩ μm2 at 1 kHz and results in unrivalled charge injection limit of 10.03 mC/cm2 when compared to other reported organic electrode nanomaterials. Furthermore, amperometric detection performances were determined for the neurotransmitters dopamine and serotonin, exhibiting linear concentration range from 0.1 to 9 μM and from 0.06 to 9 μM respectively, high sensitivities (44.54 pA/nM.μm2 and 71.08 pA/nM.μm2, respectively) and low detection limits (0.045 μM and 0.056 μM, respectively). Cell viability was investigated on PEDOT:CNF coated microelectrodes to show that the composite material does not advocate any cytotoxicity. Taken together, these results suggest the great potential of PEDOT:CNF composite for developing next-generation multifunctional microelectrodes for applications in neural therapies.