A series of rhodol‐; fluorescein‐ and rhodamines‐based spirolactam compounds, bearing electron donor amines have been prepared. For this purpose we have redesigned the synthesis of the rhodol scaffold using 2‐(2,4‐dihydroxybenzoyl)benzoic acid obtaining one example rhodol methyl ester in good yields (25–30 %) Thus, one set of non‐cytotoxic rhodamine‐based compounds has been prepared using thermal and microwave assisted synthesis (40–78 %) and tested as high affinity ATP chemo‐sensors.