This article provides a general overview of the most relevant topics in the applications of BINOL modified at the 3 and 3′-positions in asymmetric catalysis. A brief introduction to the chiral BINOL backbone so modified is given. A selection of the most outstanding uses of the catalysts according to the functional groups at the 3,3′-positions of BINOL backbones such as 3,3′-disubstituents of BINOLs, phosphoric acid derivatives and phosphoramidites is then presented. This review aims to introduce the latest developments of this active field, including the literature since 2008.