The distribution of dopants has significant influence on the electronic property of semiconductors. However, in a homogeneous crystalline material, the occupation of dopants is usually randomly distributed. Using the generalized Bloch theorem, we show that a twisting deformation has a pronounced impact on the distribution of dopants in single-crystalline Si nanowires (SiNWs). With systematic calculations, we find that the dopant atoms with smaller sizes than the host Si atom prefer atomic sites near the NW core, while dopants of larger sizes are prone to staying around the NW surface. The underlying mechanism of this intriguing phenomenon is related to the inhomogeneous shear strain along the NW radial direction. Such a trend is nearly independent of dopants with different numbers of valence electrons and also independent of the detailed crystal structures of NWs. Our findings provide an effective approach to control the dopant distribution in semiconductors, which is critical for the design of devices with reproducible electronic properties.