Silicon nanowires (NWs) could enable low-cost and efficient photovoltaics, though their performance has been limited by nonideal electrical characteristics and an inability to tune absorption properties. We overcome these limitations through controlled synthesis of a series of polymorphic core/multishell NWs with highly crystalline, hexagonally-faceted shells, and well-defined coaxial p-type∕ n-type (p∕n) and p∕intrinsic∕n (p∕i∕n) diode junctions. Designed 200-300 nm diameter p∕i∕n NW diodes exhibit ultralow leakage currents of approximately 1 fA, and open-circuit voltages and fillfactors up to 0.5 V and 73%, respectively, under one-sun illumination. Single-NW wavelength-dependent photocurrent measurements reveal size-tunable optical resonances, external quantum efficiencies greater than unity, and current densities double those for silicon films of comparable thickness. In addition, finite-difference-time-domain simulations for the measured NW structures agree quantitatively with the photocurrent measurements, and demonstrate that the optical resonances are due to Fabry-Perot and whispering-gallery cavity modes supported in the high-quality faceted nanostructures. Synthetically optimized NW devices achieve current densities of 17 mA∕cm 2 and power-conversion efficiencies of 6%. Horizontal integration of multiple NWs demonstrates linear scaling of the absolute photocurrent with number of NWs, as well as retention of the high open-circuit voltages and short-circuit current densities measured for single NW devices. Notably, assembly of 2 NW elements into vertical stacks yields short-circuit current densities of 25 mA∕cm 2 with a backside reflector, and simulations further show that such stacking represents an attractive approach for further enhancing performance with projected efficiencies of >15% for 1.2 μm thick 5 NW stacks.nanodevices | nanomaterials | nanophotonics | optical nanocavities | solar cells N anostructures and nanostructured materials may enable next-generation solar cells by providing for efficient charge separation (1-16) and tunable optical absorption (11,(17)(18)(19). Semiconductor nanowires (NWs) have exhibited promising efficiencies as single NW photovoltaic elements (8)(9)(10)(11)(20)(21)(22) and as vertical arrays configured as photovoltaic (23-26) and photoelectrochemical (27, 28) solar cells, where the vertical array has been used to enhance light absorption (29). In the case of Si-based nanostructures, where Si photovoltaics represent benchmark systems with attractive material abundance and cost (30), the efficiency of NW devices has typically been limited by poor electrical performance and lack of tunable control of absorption properties at specific and broadband wavelengths. For example, previous reports of coaxial (8) and axially modulated (9) p-i-n single-NW photovoltaic devices yielded open-circuit voltages (V OC ) below 0.29 V, and, for coaxial devices, large leakage currents >1 pA. Furthermore, to accurately identify potentially unique absorption modes through photocurrent spectra ...