Polyelectrolyte multilayer capsules have become a novel and promising class of hybrid materials with great potential since they can be applied in various areas, such as pharmaceutical sciences, biotechnology, and biomedicine. The concept of using such carriers for biology application is diagnosis and treatment of diseases for convenience, safety and specific targeting. Therefore, the development of biocompatible, biodegradable and specific characteristic nanostructure material is highly desirable. Much effort has been devoted to exploring innovative and effective techniques to fabricate such materials. Among the available techniques, layer-by-layer (LbL) assembly capsules have attracted considerable attention attributing to the flexibly controlled size, shape, composition, wall thickness and functions. Protein, as the large class of biomacromolecules, was incorporated into capsules for improving the biocompatibility and specific function. In this review we provide an overview of the recent progress in biomacromolecular capsules or core/shell architecture with different diameters for the variety of purposes. The size ranging from micro-, sub-micro to nano scale based on the choice of the template. Their advantages are discussed here. The applications of these biomacromolecular capsules in biotechnological fields have also been summarized, for instance blood substitute, ATP carriers, photodynamic therapy and nanomedicines. (C) 2016 Elsevier B.V. All rights reserved.