Photophysics and proton transfer dynamics of an eminent anticancer drug, ellipticine (EPT), have been investigated inside a biocompatible octyl-β-d-glucoside (OBG) micellar medium using steady state and time-resolved fluorescence spectroscopic techniques. EPT exists as protonated form in aqueous solution of pH 7. When EPT molecules are encapsulated in OBG micelles, protonated form is converted to neutral form in the ground state due to the hydrophobic effect of the micellar environment. Interestingly, steady state fluorescence results indicate the existence of both neutral and protonated forms of EPT in the excited state, even though neutral molecules are selectively excited, and it is attributed to the conversion of neutral to protonated form of EPT by the excited state proton transfer (ESPT) process. A clear isoemissive point in the time-resolved area normalized emission spectra (TRANES) further supports the excited state conversion of neutral to protonated form of EPT. Notably, this kind of proton transfer dynamics is not observed in other conventional micelles, such as, SDS, Triton-X and CTAB. Therefore, the observed ESPT dynamics is believed to be an outcome of combined effects of the local dielectric constant felt by EPT and the local proton concentration at the OBG micellar surface. © the Partner Organisations 2014.