The photophysical behaviour of the oxadiazolyl (PBD) and diphenylamino (TAD) substituted spirobifluorenes 2′,7′-bis-(N,N-diphenylamino)-2-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)-9,9′-spirobifluoren (spiro-DPO) and 2′,7′-bis-(N,N-diphenylamino)-2-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)-9,9′-spirobifluoren (spiro-MeO-DPO) has been investigated by temperature-dependent steady-state absorption and luminescence spectroscopy and gated measurements. Fluorescence and phosphorescence lifetime measurements, relative quantum yields and dipole moments of the excited states have been determined. Asymmetrically substituted spirobifluorenes exhibit charge-transfer (CT) emission due to coupling (spiroconjugation) between the fluorene fragments of spirobifluorene. They show a considerable ground-state dipole moment and exist as equilibrating conformeres. Population of the CT state only occurs after absorption to the locally excited singlet state. The CT fluorescence is dominated by the emission of two equilibrating conformeres with similar dipole moments. At low temperature they planarize in both molecular halves and show strong phosphorescence that is still detectable at room temperature.