The poor antiwear properties of Ti–6Al–4V have restricted its applications as biomedical materials. In this work, microgrooves with different groove width and graphene oxide (GO) coating were constructed on the surface of Ti–6Al–4V by laser processing and chemical assembly, respectively. The effects of microgroove width on the anticorrosion and biotribological properties of GOs-coated Ti–6Al–4V alloys were systematically investigated. The results indicate that the GOs-coated sample with 45 μm groove width (Ti-45-GO) can effectively improve the anticorrosion of Ti–6Al–4V, due to the surface microstructure homogenization from Ti−45 substrate and the shielding effect of GO coatings. Furthermore, the Ti-45-GO sample exhibits excellent antiwear properties, owing to the capture of wear debris of microgrooves and the high strength and resilience from GO coatings. Display omitted •GOs-coated laser microgrooved Ti–6Al–4V with different groove width are prepared.•The effects of groove width on anticorrosion and antiwear of Ti–6Al–4V are studied.•Groove width of 45 μm can better enhance anticorrosion and antiwear of Ti–6Al–4V.•The anticorrosion and biotribological mechanisms were both discussed.•The treatment can be used to improve anticorrosion and antiwear of other materials.