The nanostructure optimisation of metal oxides is of crucial importance to exploit their qualities in artificial photosynthesis, photovoltaics and heterogeneous catalysis. Therefore, it is necessary to find viable and simple fabrication methods to tune their nanostructure. Here we reveal that graphene oxide flakes, known for their nano- and two-dimensionality, can be used as a sacrificial support to replicate their nano- and two-dimensionality in photocatalytic titania. This is demonstrated in the calcination of Ti16O16(OEt)32 polyoxotitanium clusters together with graphene oxide flakes, which results in pure titania nanoflakes of <10 nm titania nanoparticles in a two-dimensional arrangement. These titania nanoflakes outperform the titania prepared from only Ti16O16(OEt)32 clusters by a factor of forty in the photocatalytic hydrogen production from aqueous methanol suspensions, as well as the benchmark P25 titania by a factor of five. These outcomes reveal the advantage of using polyoxotitanium clusters with graphene oxide and open a new avenue for the exploitation of the vast variety of polyoxometalate clusters as precursors in catalysis and photovoltaics, as well as the use of graphene oxide as a sacrificial support for nanostructure optimisation.