Spurred by controversial literature findings, we encapsulated reduced graphene oxide (rGO) in ZnO hierarchical microstructures (rGO loadings spanning from 0.01 to 2 wt%) using an in situ synthetic procedure. The obtained hybrid composites were carefully characterized, aiming at shining light on the possible role of rGO on the claimed increased performance as photocatalysts. Several characterization tools were exploited to unveil the effect exerted by rGO, including steady state and time resolved photoluminescence, electron microscopies and electrochemical techniques, in order to evaluate the physical, optical and electrical features involved in supporting the catalytic degradation of rhodamine B in water.Several properties of native ZnO structures were found changed upon the rGO incapsulation (including optical absorbance, concentration of native defects in the ZnO matrix and double-layer capacitance), which are all involved in determining the photocatalytic performance of the hybrid composites. The findings discussed in the present work highlight the high complexity of the field of application of graphene-derivatives as supporters of semiconducting metal oxides functionality, which has to be analyzed through a multi-parametric approach.