Physical and chemical technologies have been continuously progressing advances of neuroscience research. The development of research tools for closed-loop control and monitoring neural activities in behaving animals is highly desirable. In this paper, we introduce a wirelessly operated, miniaturized microprobe system for optical interrogation and neurochemical sensing in the deep brain. Via epitaxial liftoff and transfer printing, microscale light emitting diodes (micro-LEDs) as light sources, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated diamond films as electrochemical sensors are vertically assembled to form implantable optoelectrochemical probes, for real-time optogenetic stimulation and dopamine detection capabilities. A customized, lightweight circuit module is employed for untethered, remote signal control and data acquisition. Injected into the ventral tegmental area (VTA) of freely behaving mice, in vivo experiments clearly demonstrate the utilities of the multifunctional optoelectrochemical microprobe system for optogenetic interference of place preferences and detection of dopamine release. The presented options for material and device integrations provide a practical route to simultaneous optical control and electrochemical sensing of complex nervous systems.