During the last 50 years, the minimally invasive techniques for monitoring brain chemistry in vivo have significantly contributed to our current understanding of chemical neurotransmission in relation to behavior, as well as, to neuropathology and neuropharmacology of CNS disorders. This article provides a short historical overview of implantable devices including voltammetric electrodes, biosensors, microdialysis and related analytical techniques developed for monitoring and sampling brain chemistry in experimental disease models. A special emphasis is given to dopamine, which besides its important role as a neurotransmitter, could be readily detected by electrochemical techniques. Today, about 70% of all published papers applying voltammetry in the brain refer to dopamine monitoring; the corresponding percentage of brain microdialysis papers referring to dopamine is 41%.