Can single crystalline materials be used for low dimensional p-n junction design? This is an open and long-standing problem. Microscopic simulations based on the generalized Bloch theorem show that in single crystalline Si nanowires, an axial twist can lead to the separation of p-type and n-type dopants along the nanowire radial dimension, and thus realizes the p-n junction. A bond orbital analysis reveals that this is due to the twist-induced inhomogeneous shear strain in the nanowire.