III-V nanowires (NWs) have a great potential for solar energy applications due to their diameter-dependent optical properties, which may enhance absorption of light. In addition, core-shell radial p-i-n structures, in which the direction of light absorption is orthogonal to the carrier collection, can provide efficient carrier collection. The main goal of this thesis is the experimental study of the challenges of NW-based solar cells, related to materials and device fabrication. In the first part of the thesis, we present an analysis of where the electrical losses can be originated. By applying an equivalent circuit analysis approach, we classified them into three main groups: (i) the non-uniformity of NWs which may result in a reduction of the parallel resistance, (i) potential barriers originated at the different materials interfaces in the solar cell structure may result in an increase of the series resistance or addition of a second diode and (iii) surface recombination resulting in the reduction of the open-circuit voltage. In this thesis, we propose separate strategies to characterize and tackle these factors. The electric scheme of a NW-based solar cell consists of an ensemble of p-n junctions connected in parallel. We show how conductive-probe atomic force microscopy, C-AFM, is an essential tool for the characterization and optimization of these parallel-connected NW devices. We demonstrate topography and current mapping of the NW arrays, combined with current-voltage (IV) measurements of the individual NW junctions from the ensemble. Our results provide discussion elements on some of the factors limiting the performance of a NW-based solar cell, such as uniformity and photosensitivity of the individual NW p-n junctions within the array, and thereby a path for their improvement. Besides parallel losses due to uniformity issues, barriers in the carrier collection through the various heterointerfaces composing the device is discussed. To analyze it, we illuminate GaAs NW-based solar cells at different levels of light intensity and extract IV characteristics. This analysis helps to separately study the NW p-n junction response and the series resistance. The high series resistance of the NW-ensemble device can be attributed to the following interfaces: 1) GaAs-ITO, forming a photoactive Schottky diode, which suppresses the p-n junction at high concentrations of light, and 2) Si-GaAs heterojunction, disturbing the flow of majority carriers. Finally, the characterization of surface passivation in high-aspect-ratio nano/micro structures is addressed by electrochemical impedance spectroscopy (EIS). The method is applied to Si micropillars, as a proof-of-concept prior to the application to III-V nanowires. We tested structures passivated by a dielectric layer. The effect of different surface treatments on the interface state density were quantified by the analysis of the capacitance-voltage and conductance-voltage characteristics. This method allows the electrical measurements on rough vertical surfaces, which would otherwise suffer from high gate leakage currents if tested using solid-state metal-insulator-semiconductor scheme. The results and characterization methods, demonstrated in this work, contribute to the overall efforts of the scientific community on how to reveal the main engineering challenges in NW-based solar cells. It thus paves the way to approach the fundamental conversion efficiencies predicted by theory.