Extracellular vesicles (EVs) are membrane-bound vesicles extruded in substantial quantities from living healthy and cancerous cells into body fluids, show great promise for the early detection and monitoring of cancer. However, all of the current methods for EV isolation and post-delivery still suffer from one or more of: low efficiency, low specificity, sample volume limitations, cost, complexity for the user and captured EVs damage. Herein, we demonstrate the fabrication of a class of multifunctional bio-interfaces for selective capture/release of EV subpopulations with particular surface determinants. This was achieved by the functionalization of our device with aptamers specific to EV markers. The biofunctionality, high surface area and surface functionality of the developed device enable the selective capture of EVs from large sample volumes and their subsequent controlled release into a small volume. We believe the developed methodology will open new vistas in the design of multifunctional smart bio-materials with many applications in extracellular research and cancer diagnosis.