A Langmuir film of a third-generation earbazole-terminated poly(benzyl ether) (G3-CtPBE) dendrimer was investigated at the air water interface. Langmuir-Blodgett (LB) films were deposited on gold substrates and investigated by atomic force microscopy (AFM), followed by electrochemical and electronanopatterning studies. For the G3-CtPBE dendrimer aggregates, variable concentration and surface pressure gave control over aggregate size and shape at the air water interface. At a lower concentration Cl, aggregate spherical nanoparticles were observed with a face-on or overlapped orientation with increasing surface pressure. However, at a higher concentration C2, their surface morphologies exhibited circular and rod-shaped aggregates with respect to increasing surface pressure attributed to an edge-on configurational change. Moreover, in situ simultaneous interfacial potentiostatic electrodeposition with LB transfer at the air water interface was employed for the First time with the G3-CtPBE dendrimers onto a hydrophilic surface under constant voltage (i.e., close to the oxidation potential of G3-CtPBE for electrochemical cross-linking). Electrochemical cross-linking on G3-CtPBE dendrimer LB films was also performed ex situ to investigate electrochemical and optical properties. Finally, as an application of a cross-linkable LB Film, electronanolithography was carried out to prepare nanopatterns using the current sensing atomic force microscopy (CS-A FM) technique.