Recent advances in the discovery and development of new nickel-catalyzed processes will be described. Illustrations in the reductive coupling of unsaturated components and in the development of new transformations of easily accessible phenol derivatives will be provided. In these areas, our recent efforts have focused on the design of regiodivergent processes and on the development of strategies to enable regioselectivity and enantioselectivity to be simultaneously addressed in catalytic transformations. Mechanistic studies are providing considerable insight into the origins of selectivity and reactivity in the processes under development. In addition to the focus on catalysis by nickel-NHC complexes, the lecture will also describe recent collaborative work in biocatalysis using cytochrome P450 enzymes as an enabling tool for organic synthesis.