We report conformal, epitaxial growth of GaP layers on arrays of Si microwires. Silicon wires grown using chlorosilane chemical vapor deposition were coated with GaP grown by metal-organic chemical vapor deposition. The crystalline quality of conformal, epitaxial GaP/Si wire arrays was assessed by transmission electron microscopy and x-ray diffraction. Hall measurements and photoluminescence show p- and n-type doping with high electron mobility and bright optical emission. GaP pn homojunction diodes on planar reference samples show photovoltaic response with an open circuit voltage of 660 mV
