The mobility of charge carriers across a semiconductor nanoparticle based 3D network (i.e. a gel) and the interfacial transfer of the charge carriers across the nanoparticle network/electrolyte boundary are elementary processes for applications in the fields of sensing and energy harvesting. The automated manufacturing of electrodes coated with porous networks can already be realized by inkjet printing. By simultaneous printing of CdSe/CdS dot-in-rod shaped nanorods (NRs) and the destabilization reagent, CdSe/CdS gel network coated electrodes can be obtained. In the presented work, the charge carrier mobility of the electrons and the holes within the porous CdSe/CdS nanorod gel network are investigated via photoelectrochemistry. Under application of linear sweep voltammograms (LSVs) and intensity modulated photocurrent spectra (IMPS) it is shown, that the electron is moving within the tip-to-tip connected CdSe/CdS NR gel structure, while the holes are trapped in the CdSe seed of the semiconductor heterostructures. Furthermore, the preparation process of gel structures is related to the elementary mechanism of hydration, which can be shown via photoelectrochemical long term studies.