Understanding the fundamental processes that govern charge transfer at semiconductor/liquid interfaces is paramount for the efficient operation of photoelectrochemical systems. Quantitative voltammetric studies at macroscopic semiconductor electrodes have long been hindered by the lack of a complete analytical expression for the current-potential response and contribution from defect-induced surface states. This presentation will highlight the recent application of recessed semiconductor ultramicroelectrodes to voltammetric measurements of heterogeneous charge transfer rate constants, band edge positions, and diode quality factors at semiconductor/liquid interfaces. Three aspects will be discussed. First, a general description of the observed current-potential response will be provided along with considerations necessary for extraction of kinetic and energetic information. Second, measured charge transfer rates, band edge positions, and diode quality factors at poised and unpoised microscopic Si/electrolyte contacts with varying crystal orientation, doping, and electrolyte solutions will be presented. These results will be placed in the context of previous measurements at macroscopic Si/liquid contacts. Third, an overview of unique opportunities afforded through use of microscopic and nanoscopic semiconductor/liquid contacts will be given, with an emphasis on investigating charge transfer theories.