The role of reduced dimensionality and of the surface on electron-phonon (e-ph) coupling in silicon nanowires is determined from first principles. Surface termination and chemistry is found to have a relatively small influence, whereas reduced dimensionality fundamentally alters the behavior of deformation potentials. As a consequence, electron coupling to 'breathing modes' emerges that can not be described by conventional treatments of e-ph coupling. The consequences for physical properties such as scattering lengths and mobilities is significant: the mobilities for [110] grown wires is 6 times larger than for [100] wires, an effect that can not be predicted without the form we find for Si nanowire deformation potentials.Silicon nanowires, beyond having been successfully demonstrated as conventional semiconductor devices, 1-4 are beginning to be seen as the important blocks for novel energy harvesting applications, such as solar cells 5,6 and efficient thermoelectric devices. 7,8 All these applications rely on a high electronic conductivity of electrons, while in the latter a low phonon conductivity is also essential. 9,10 At the heart of understanding the interrelation between these properties is the interaction of phonons and electrons: scattering of electrons with phonons reduces the conductivity of these devices, increasing heating and reducing their efficiency, while the scattering