Self-assembled monolayers (SAMs) of metal complexes are a central component of functional chemical systems for energy conversion like in e.g. the dye-sensitized photoelectrochemical solar cells or photocatalytic processes at semiconductor surfaces. In this context, scanning electrochemical microscopy (SECM) under illumination is a most valuable tool for the understanding of elementary processes of such systems. SECM comprises an ultra-microelectrode (UME), which is incorporated into a 3- or 4-electrode, respectively, electrochemical setup and which can be positioned with sub-micrometer resolution in 3 dimensions relative to a substrate. In our system, we used Pt-UMEs and dye-sensitized nano-structured electrodes as substrates. The substrate can be illuminated from the backside, which resembles working conditions of solar cell arrangements. The electrolyte consists of 2-methoxypropionitrile in conjunction with redox couples as they are used in dye-sensitized nano-structured solar cell. With this setup the photoelectrochemistry in close contact to the substrate surface initiated by the injection of electrons from the dye into the conduction band of the TiO2 due to illumination at working conditions has been investigated. In this contribution we present the general principle of the method as well as an initial validation by relating photocurrents measured with the SECM and solar cell performances.