Developing metallic nanocatalysts with high reaction activity, selectivity and practical durability is a promising and active subfield in electrocatalysis. In the classical "bottom-up" approach to synthesize stable nanomaterials by chemical reduction, stabilizing additives such as polymers or organic surfactants must be present to cap the nanoparticle to prevent material bulk aggregation. In recent years, biological systems have emerged as green alternatives to support the uncoated inorganic components. One key advantage of biological templates is their inherent ability to produce nanostructures with controllable composition, facet, size and morphology under ecologically friendly synthetic conditions, which are difficult to achieve with traditional inorganic synthesis. In addition, through genetic engineering or bioconjugation, bio-templates can provide numerous possibilities for surface functionalization to incorporate specific binding sites for the target metals. Therefore, in bio-templated systems, the electrocatalytic performance of the formed nanocatalyst can be tuned by precisely controlling the material surface chemistry. With controlled improvements in size, morphology, facet exposure, surface area and electron conductivity, bio-inspired nanomaterials often exhibit enhanced catalytic activity towards electrode reactions. In this Review, recent research developments are presented in bio-approaches for metallic nanomaterial synthesis and their applications in electrocatalysis for sustainable energy storage and conversion systems.