Proteoglycan (PG) is an important extracellular matrix (ECM), which is composed of long unbranched, and highly negatively chard glycosaminoglycan (GAG) chains. G The PGs showed a ‘bottlebrush’ like structure that the GAGs were covalently attached to the hyaluronic acid (HA) backbone, which fill the space of collagen meshwork. In common musculoskeletal diseases such as disc degeneration and osteoarthritis, typical pathophysiological changes include significant loss of GAG, followed by loss of the normal function of tissues. Here, we aimed to fabricate a biomimetic scaffold for GAG‐rich tissue, such as nucleus pulposus with the GAG/ hydroxyproline (HYP, marker of collagen, 13.5% w/w of the collagen) ratio of 27:1. And we hypothesized that mimicking the GAG content by chemically modifying certain ECM components, including collagen (Col) and hyaluronic acid (HA) to positively charged, is possible to fabricate a scaffold that mimics the complex ECM of GAG‐rich tissues. In this work, we demonstrated the fabrication of the biomimetic scaffold, aminated collagen (aCol)‐aminated HA(aHA)‐ GAG. The fabricated aCol‐aHA‐GAG showed a high and controllable GAG/HYP ratio up to 39.1:1, achieving the quality of GAG‐rich tissue as that of young adult NP (27:1). The aCol‐aHA‐GAG scaffold showed biomimetic ‘nanobeads’ like structure in SEM and ‘bottlebrush’ structure under TEM, recapitulating the ultrastructure of the native disc. In addition, the aCol‐aHA‐GAG maintained the bNPCs morphology and GAG content after bNPCs encapsulation. These results suggested that aCol‐aHA‐GAG was a biomimetic scaffold for NP. This work contributes to developing a biomimetic scaffold for NP tissue engineering.