Biomacromolecules play a key role in protecting human biointerfaces from friction and wear, and thus enable painless motion. Biomacromolecules give rise to remarkable tribological properties that researchers have been eager to emulate. In this review, we examine how molecules such as mucins, lubricin, hyaluronic acid and other components of biotribological interfaces provide a unique set of rheological and surface properties that leads to low friction and wear. We then highlight how researchers have used some of the features of biotribological contacts to create biomimetic systems. While the brush architecture of the glycosylated molecules present at biotribological interfaces has inspired some promising polymer brush systems, it is the recent advance in the understanding of synergistic interaction between biomacromolecules that is showing the most potential in producing surfaces with a high lubricating ability. Research currently suggests that no single biomacromolecule or artificial polymer successfully reproduces the tribological properties of biological contacts. However, by combining molecules, one can enhance their anchoring and lubricating capacity, thus enabling the design of surfaces for use in biomedical applications requiring low friction and wear.