The amphibolite-facies, Au-mineralized mafic rocks at the Plutonic Gold Mine are intruded by a suite of dolerite dykes of unknown age. The zones between these intrusive units often host significant Au mineralization. It is unclear whether this enrichment in Au mineralization is a function of the intrusion of the dolerites themselves or the influence of pre-existing structures (e.g. faults or shears). Geochemical characterization of the different microcrystalline dolerite units is important to the understanding of the structural architecture of the deposit and to the possible relationship of the dolerites to Au mineralization. The collection of a large geochemical dataset (n = 497) from the dolerite dykes from across the deposit using portable X-ray fluorescence technology allows us to break them into four distinct geochemical groupings. Thus we can define their geometries with greater confidence than was possible using lithology alone. Traverses across individual dolerite dykes indicate that the chill margins are the most geochemically homogenous and most likely to represent the chemistry of the source magma. Plots of Ti v. Zr combined with principal component analysis (PCA) define four geochemically distinct suites of dolerites. By applying this understanding to dolerites in a small area of the deposit, a new interpretation was generated whereby significant amounts of rock that were previously modelled as being dolerite were reclassified as potential host-rock, thus increasing the potential for Au in this area.