As engineers strive to mimic the form and function of naturally occurring materials with synthetic alternatives, the challenges and costs of processing often limit creative innovation. Here we describe a powerful yet economical technique for developing multiple coatings of different morphologies and functions within a single textile membrane, enabling scientists to engineer the properties of a material from the nanoscopic level in commercially viable quantities. By simply varying the flow rate of charged species passing through an electrospun material during spray-assisted layer-by-layer deposition, individual fibres within the matrix can be conformally functionalized for ultrahigh-surface-area catalysis, or bridged to form a networked sublayer with complimentary properties. Exemplified here by the creation of selectively reactive gas purification membranes, the myriad applications of this technology also include self-cleaning fabrics, water purification and protein functionalization of scaffolds for tissue engineering.