Synthetic polymers and gels capable of molecular recognition are very useful in designing novel intelligent biomaterials. In this article we review the recent progress in both theoretical and experimental studies toward making heteropolymers and gels with biomimetic properties, specifically in relation to protein recognition. Knowledge obtained from protein-folding studies sheds much light on our understanding of the heteropolymer behavior. Consequently, it is possible to design synthetic heteropolymers with specific structure that can fold into unique conformations, form receptor-like cavities and recognize specific target molecules. Recent studies towards simplifying the requirement for the heteropolymer structures and the polymerization procedures are reviewed. Intelligent polymer gels can be designed with new and interesting characteristics of molecular imprinting. The results are encouraging for further investigation and design of synthetic gels with programmable collapsed structure might be achieved.