A large thermoelectric power factor in heavily boron-doped p-type nanograined Si with grain sizes ∼30 nm and grain boundary regions of ∼2 nm is reported. The reported power factor is ∼5 times higher than in bulk Si. It originates from the surprising observation that for a specific range of carrier concentrations, the electrical conductivity and Seebeck coefficient increase simultaneously. The two essential ingredients for this observation are nanocrystallinity and extremely high boron doping levels. This experimental finding is interpreted within a theoretical model that considers both electron and phonon transport within the semiclassical Boltzmann approach. It is shown that transport takes place through two phases so that high conductivity is achieved in the grains, and high Seebeck coefficient by the grain boundaries. This together with the drastic reduction in the thermal conductivity due to boundary scattering could lead to a significant increase of the figure of merit ZT. This is one of the rare observations of a simultaneous increase in the electrical conductivity and Seebeck coefficient, resulting in enhanced thermoelectric power factor.