Unconventional zigzag indium phosphide (InP) single-crystalline and twinned nanowires were produced via thermal evaporation of indium phosphide in the presence of zinc selenide. The structure and morphology of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Studies found that two type of nanowires exist in the products, namely, the periodic-rhombus-decorated single-crystalline InP (type I) nanowires and jagged twinned InP (type II) nanowires. Both of them have preferential < 111 > growth directions. The optical properties were also investigated at room temperature, and they show that the nanowires display a strong emission at similar to 750 nm, which is quite different from that observed in all previous reports related to the InP nanostructures.