Porous carbon materials such as activated carbon have applications in electrodes and sensors. Though they provide high surface areas and porosity, they are not always able to make strong connections to increase conductivity with other active materials. Graphene and graphite are highly conductive materials but lack surface area and porosity. Herein we propose a novel material synthesized from simple esterified carbohydrate-polymer precursors which exhibit both graphite/graphene sheets and porous, amorphous carbon structures. The carbohydrate-polymer precursor is used to grow graphene and graphite sheets on a Ni sputter coated Si/SiO2 substrate. Such a precursor allows an oxidation product to undergo esterification with poly(vinyl) alcohol and grow porous carbon structures. Spin coating distributes the product solution over the substrate and annealing in reducing atmosphere allows the Ni thin film to dissolve carbon feedstock and thus grow 2D graphene and graphite sheets directly bonded to a 3D network of porous carbon structures. Porous morphology is identified by SEM and analyzed by BET. XRD showing graphite and graphene growth on Ni substrate is collaborated with RAMAN spectroscopy. I-V curves indicate Ohmic contact between the substrate and the Porous Graphene Nanoarchitecture. Such a novel material shows promising applicability in capacitors and battery electrode materials.