This review summarizes the biosynthesis, cell type-distribution and function of brain aromatase cytochrome P450 (P450aro) and 5alpha-reductase enzymes. This overview covers the impact of the steroid products of the P450aro and 5alpha-reductase enzymes in establishing sexually dimorphic brain structures, specifically the sexually dimorphic nucleus of the preoptic area (SDN) and the anteroventral periventricular nucleus (AVPV). Additionally, since metabolites of the P450aro and 5alpha-reductase enzymes are known to regulate the calcium-binding protein, calbindin (CALB), CALB is reviewed in relationship to its potential role in determining sexually dimorphic brain structures. Finally, recent reports indicate that phytoestrogens inhibit P450aro and 5alpha-reductase activities in peripheral tissue sites, therefore, the effects of phytoestrogens on brain P450aro and 5alpha-reductase are briefly considered and the impact of consuming a high vs. a low phytoestrogen diet on visual spatial memory in male and female rats is presented.