Fluorescence quenching of rhodamine 6G by graphene oxide (GO) was investigated using steady‐state fluorescence spectroscopy and ultrafast time‐resolved absorption spectroscopy. The steady‐state fluorescence spectra showed that rhodamine 6G fluorescence was effectively quenched by titrating the GO to the rhodamine 6G solutions. For lower GO concentrations, transient dynamic curves followed two‐exponential decay parameters. For higher GO concentrations, the dynamic curves could not be fitted well, and three‐exponential decay parameters were appropriate. The results indicated that there was a new transition process (electron transfer) in the exited rhodamine 6G and GO solution.