AbstractThe synthesis and characterization of two thiophenol‐modified fluorographene derivatives, namely methoxythiophenol‐and dimethylaminothiophenol‐modified fluorographenes, are reported, while their third‐order nonlinear optical response were thoroughly investigated under both visible (532 nm) and infrared (1064 nm) with 35 ps and 4 ns laser pulses. The graphene derivatives were obtained by partial nucleophilic substitution/reduction of fluorographene by the corresponding organic thiophenols, and were fully characterized by techniques including infrared/Raman spectroscopy, X‐ray photoelectron spectroscopy, atomic force spectroscopy, and high‐resolution transmission microscopy. This type of modification resulted in graphenic structures where the attached thiol groups, sp2 domains, and the residual fluorine groups act as donors, π bridges, and acceptors, respectively. Both derivatives exhibited large nonlinear optical response compared to fluorographene, and have potential applications in optical limiting as an alternative to fullerenes.