A convenient methodology for the synthesis of photolabile crosslinked hyperbranched polyglycerol nanocapsules is presented. These nanocarriers selectively and efficiently bind ionic guest molecules. The stability of the host-guest complexes formed depends on the counterion of the guest molecules. Moreover, the control over guest binding can be achieved by modification of the polymer building blocks, in particular the outer shell. In addition, photo-triggered degradation of the nanocarrier leads to efficient release of encapsulated guest molecules. This approach, using photolabile dendritic nanocarriers to bind and release guest molecules, is of particular relevance for biomedical applications where selective guest binding and controlled release are crucial.