Crystalline Si wires, grown by the vapor–liquid–solid (VLS) process, have emerged as promising candidate materials for low-cost, thin-film photovoltaics. Here, we demonstrate VLS-grown Si microwires that have suitable electrical properties for high-performance photovoltaic applications, including long minority-carrier diffusion lengths (L_n ≫ 30 µm) and low surface recombination velocities (S ≪ 70 cm·s⁻¹). Single-wire radial p–n junction solar cells were fabricated with amorphous silicon and silicon nitride surface coatings, achieving up to 9.0% apparent photovoltaic efficiency, and exhibiting up to 600 mV open-circuit voltage with over 80% fill factor. Projective single-wire measurements and optoelectronic simulations suggest that large-area Si wire-array solar cells have the potential to exceed 17% energy-conversion efficiency, offering a promising route toward cost-effective crystalline Si photovoltaics.