This first-attempt study used electrochemical methods to quantitatively assess electron-shuttling capabilities of different neurotransmitters crucial to catecholamine biosynthesis in human brain. As prior studies mentioned, aromatics bearing ortho- or para-dihydroxybenzenes could reveal promising electroactivities to stimulate bioenergy generation in microbial fuel cells (MFCs). This feasibility study extended to investigate the electrochemical characteristics of catecholamines and trace amines (e.g., 14 model compounds selected from neurotransmitters) synthesized by human brain via cyclic voltammetry methods (CVs) and MFCs. Dopamine (DA), levodopa (L-DOPA), epinephrine (EP), norepinephrine (NP), and 3,4-dihydroxyphenylacetic acid (DOPAC) would perform the electron-shuttling characteristics, and the rest would not. In particular, DA formed by decarboxylation of L-DOPA could exhibit relatively higher electrochemical activities than their precursors. In addition, carboxylic acids formed by deamination and carboxylation of trace monoamines would reveal more significant reductive potential (E-pc); however, their oxidative electric currents seemed to be reduced. That is, chemical structure significantly influenced whether the electrochemical characteristics could be effectively expressed. This work also clearly revealed that neurotransmitters with ortho-dihydroxybenzenes exhibited promising stimulation to bioelectricity-generating capabilities of MFCs in the ranking of DA EP > NP > L-DOPA > DOPAC. This was consistent with ES behaviors as CV analyses indicated.