A four-component reaction strategy for access to acyclic nitrile-substituted all-carbon quaternary centers is disclosed. In the presence of a DABCO-based ionic liquid catalyst, the reactions proceed smoothly with a wide range of substrates efficiently to deliver nitrile-substituted all-carbon quaternary centers under mild reaction conditions. This protocol is further demonstrated as an efficient method for the construction of contiguous all-carbon quaternary centers. All the reactions are easily operated in a green manner, producing water as the only byproduct. Some of the products show excellent activity against specific fungi.