Molecular mobility of the symmetric carbocyanine fluorophore DTDCI was studied in AOT/alkane reverse micelles containing non-aqueous polar liquids DMF, formamide, ethylene glycol and glycerol by monitoring both the torsional photoisomerization and rotational reorientation, both of which were sensitive to microviscosity of the local environment. The DTDCI fluorophore resides completely within the AOT-polar liquid reverse micelle nano-droplets, where its dynamics were found to be significantly retarded irrespective of the polar liquid taken, due to a combination of electrostatic and hydrophobic forces that induce the guest DTDC+ cation to attach to the AOT molecules of the host droplet. The addition of strong hydrogen-bond donating polar liquids like formamide, ethylene glycol and glycerol causes a systematic enlargement of the droplets. Rotational dynamics of the fluorophore inside the nano-droplets was characterized by a diffusion coefficient comparable to that in highly viscous solvents like ethylene glycol. This journal is © The Royal Society of Chemistry and Owner Societies 2015.