Molecular beam epitaxy (MBE) via the vapor-liquid-solid (VLS) reaction was used to grow ZnSe nanowires (NWs) on (111), (100), and (110) oriented GaAs substrates. Through detailed transmission electron microscopy (TEM) studies, it was found that 〈111〉 orientation is the growth direction for NWs with size ≥30 nm, while NWs with size around 10 nm prefer to grow along the 〈110〉 direction, with a small portion along the 〈112〉 direction. These observations have led to the realization of vertical ZnSe NWs with size around 10 nm grown on a GaAs (110) substrate. An ordered ZnSe NW array fabricated on a GaAs (111) substrate with a novel prepatterning method associated with plasma etching shows a high degree of ordering and a good size uniformity of the as-grown NWs. The diameter of the NWs in the array is around 80 nm and most of them are found to orient vertically, but some tilt to one of the six possible directions of the 〈111〉 family.