Langmuir-Blodgett method has always been traditionally utilized in the deposition of two-dimensional structures. In this work however, we employed the method to deposit three-dimensional reduced graphene oxide layers using an unconventional protocol for the first time. This was achieved by carrying-out the dipping process after the collapse pressure or breaking point, which results in the formation of a highly porous three-dimensional surface topography. By varying the number of deposition layers, the porosity could be optimized from nanometer to micrometer dimensions. Employed as bioelectrodes, these three-dimensional reduced graphene oxide layers may allow improved adhesion and biocompatibility compared to the conventional two-dimensional surfaces. Higher number of pores also improves mass transport of materials and therefore increases the charge sustaining capacity and sensitivity. This could ultimately improve performance of biofuel cells and other electrode based systems.