We report the preparation, the absorption spectra, and the photophysical and photochemical properties in dichloromethane solution of four dendrimers of the poly(propylene amine) family (indicated by POPAM or PPI) functionalised with naphthalene and trans-azobenzene units. Each dendrimer Gn, where n = 1 to 4 is the generation number, comprises 2(n+1)-2 (i.e., 30 for G4) tertiary amine units in the interior and 2(n1) (i.e., 32 for G4) naphthalene and trans-azobenzene units in the periphery. For comparison purposes, the photophysical and photochemical properties of model compounds of the peripheral units have also been investigated. We have found that the fluorescence of the naphthalene units is quenched by the tertiary amines (via electron transfer) as well as by the trans-azobenzene units (via energy transfer). The quantum yields of the trans-->cis and cis-->trans photoisomerisation of the azobenzene units have been measured at various excitation wavelengths. Quenching of the fluorescence of the excited naphthalene unit by the trans- and cis-azobenzene units is accompanied by the sensitisation of the cis-->trans (but not of the trans-->cis) isomerisation. The rate constant of the thermal cis-->trans isomerisation of the azobenzene units has also been measured. Comparison of the results obtained for model compounds and for the G4 dendrimer shows that the dendritic structure favours the trans configuration of the azobenzene units ("dendritic effect"), presumably because it is less demanding in terms of space and causes less crowding on the dendrimer surface.