Trimethylboron (TMB) was investigated as a p-type dopant source for the vapor–liquid–solid growth of boron-doped silicon nanowires (SiNWs). The boron concentration in the nanowires was measured using secondary ion mass spectrometry and results were compared for boron-doping using TMB and diborane (B2H6) sources. Boron concentrations ranging from 1×1018 to 4×1019 cm-3 were obtained by varying the inlet dopant/SiH4 gas ratio. TEM characterization revealed that the B2H6-doped SiNWs consisted of a crystalline core with a thick amorphous Si coating, while the TMB-doped SiNWs were predominantly single crystal even at high boron concentrations. The difference in structural properties was attributed to the higher thermal stability and reduced reactivity of TMB compared to B2H6. Four-point resistivity and gate-dependent conductance measurements were used to confirm p-type conductivity in the TMB-doped nanowires and to investigate the effect of dopant concentration on nanowire resistivity.