Graphene oxide (GO) exfoliated sheets were used as two dimensional platforms to covalently tether on their surface thousands of optically active quaterthiophene molecules (T4), using an innovative microwave-assisted silanization reaction. This method allowed to perform GO functionalization in one-step, under mild conditions in a few tens of minutes rather than days. The hybrid GOT4 could be processed in either H2O or apolar organic solvents and deposited as single sheets, microplatelets or macroscopic membranes. Absorption/emission spectroscopy reveals that GOT4 combines limited T4-T4 interactions with strong T4-GO ones. These findings, combined with the ‘user-friendly’ engineering approach presented here, pave the way towards the bottom-up fabrication of new GO-based tailored materials for electronics, sensors and biological applications.