1IntroductionBrain is the most complicated whilst the least understood organ of human body both in its complex neuronal networks and numerous kinds of neurochemical species involved in brain functions.M odern science has seen explosion of knowledge on central nervouss ystem (CNS) thanks to the advances of various analytical techniques. Analysis of living brain is the most essentialt ou nderstanding the physiological and pathological processeso f brain while at the same time modern sciencef aced the challenges and developed somec utting edge techniques to accomplish such goals [1,2].InMay 2015, we organized aT hemedI ssue published in Analyst dedicating to very recent development of in vivo analysiso nv arious techniques and applications [3].I nt his review, we will particularly focus on the advances of electrochemicalm ethodologiesfor the analysis of living mammalian brain.CNS bears the unique featureso fb oth widespread of the molecular weight of neurochemicalsf rom large proteins/peptides of thousandst om illions of Dalton to small molecules less than 100 Dalton, and the dynamic changes of these neurochemicalsr anging from sub-second level to monthso re ven years.S uch complication of CNS challenges all analytical techniques on multiplea spectss uch as sensitivity,s electivity,t emporala nd spatial resolution. Amongt he techniques potentially employed for studying neurochemicalc hanges in CNS,e lectrochemicalm ethods are the most advantageous because they can be used to monitor fast dynamics and regulation processes of small molecules with high temporal resolution of sub-secondo r even down to sub-millisecond. Fore xample,h igh temporal resolution could be obtainedw ith fast-scan cyclic voltammetry (FSCV),w hose scan rate is usually set at several hundred volt per second. Eachs can takes less than 10 ms and hence voltammograms could be recordeda t 100 Hz frequencym aximally and, in most studies,a10 Hz recording frequency is used to combine with electrical stimulations.A sf or amperometry,w hen aconstantp otential is held, an even highert emporalr esolution could be achieved. Such high temporal resolution is the most advantageous for the investigationso nn eurotransmission processes,d uringw hich neurotransmitters release could happen within several milliseconds.Generally,m ost electrochemical methods could provide enough sensitivity to detect basal or elicited neurochemicals with bare or surface-functionalized electrodes,b ut the selectivity hinders theirw ide applications in brain research. One of the focuses of this reviewi st he strategies developed to achieve the selectivity for the detection of electrochemically activen eurochemicals with the electrodes without the useso fr ecognition units.W ew ill firstly review the classic and most widely used electrochemical methods for the detection of catecholamine in section one.A sw ill be described later, selectivity for the detectiono fc atecholamine can be achieved by taking advantage of the neurotransmitter specificity of brain regions and the dynamictime frame...