We present an overview of fundamental work on the structure of three dimensional polymer networks with Gaussian and non Gaussian chain distributions and we summarize a number of models for multiple functionality, imperfect cross links, etc. We address design and synthesis characteristics of novel crosslinked networks capable of solute and protein transport and release as well as artificial molecular structures capable of specific molecular recognition of biological molecules. Indeed, engineering the molecular design of intelligent biopolymeric networks by controlling structure, recognition and specificity is the first step in coordinating and duplicating complex biological and physiological processes. We discuss possible applications of such networks in the biomedical field for intelligent drug delivery, drug targeting, and tissue engineering. We also discuss structurally superior networks based on ATRP and ARGET polymerizations that serve as effective carriers for siRNA delivery.