A series of different generation PAMAM dendrimers with sulforhodamine B covalently attached to the dendrimer core was investigated regarding their optical properties. Steady-state and time-resolved spectroscopic techniques were used to determine the size influence of the dendrimers on the photophysical behavior of the luminescent core. New blue emissive species were formed as the generation increased from zero to four. The growth of the dendritic branches resulted in a rise of fluorescence quantum yield and fluorescence lifetime values. Rotational correlation times were used to determine the hydrodynamic diameters of the fluorescent-core dendrimers, and good accordance was found with the values previously reported for unlabeled PAMAM dendrimers, which makes them potentially suitable diagnostic tools for biomedical tracing.