The ab-initio theory of charge transport in semiconductors typically employs the lowest-order perturbation theory in which electrons interact with one phonon (1ph). This theory is accepted to be adequate to explain the low-field mobility of non-polar semiconductors but has not been tested extensively beyond the low-field regime. Here, we report first-principles calculations of the electric field-dependence of the electron mobility of Si as described by the warm electron coefficient, β.Although the 1ph theory overestimates the low-field mobility by only around 20%, it overestimates β by over a factor of two over a range of temperatures and crystallographic axes. We show that the discrepancy in β is reconciled by inclusion of on-shell iterated 2-phonon (2ph) scattering processes, indicating that scattering from higher-order electron-phonon interactions is non-negligible even in non-polar semiconductors. Further, a ∼ 20% underestimate of the low-field mobility with 2ph scattering suggests that non-trivial cancellations may occur in the perturbative expansion of the electron-phonon interaction.