An unconventional and straightforward route to fabricate morphology-control led 2D ordered carbonaceous nanoarrays is presented. This route is based on the electron irradiation of a polystyrene colloidal monolayer followed by thermal decomposition. This strategy has the advantages of low-cost fabrication and manipulation compared to conventional lithography technique and furthermore overcomes the disadvantage of the self-assembly technique that generally has the defect of irregular units in ordered arrays. Various with irregular units, including network-like and star-like ordered arrays as well as hexagonal non-close-packed arrays, were fabricated by this novel route. These ordered arrays can be used as templates or masks to fabricate other ordered structures and then can be removed completely by thermal decomposition at a high temperature. Additionally, these arrays are carbonaceous materials that have higher thermal stability and higher refractive index compared with those of the pristine polymer, which are important for real applications such as optical devices. This method might also be used for the fabrication of other unique ordered arrays if different polymer precursor materials are used.