3D printing technologies have expanded the possibilities of fabricating new composite materials with tailored properties, which depend on both the materials selected and the structural design at multiple length scales. Here, a catalyst-free CVD method has been used to produce hybrid materials based on 3D printed cellular α-Al2O3 substrates decorated by either nanocrystalline graphene or nanocrystalline graphitic films of tunable number of layers. Graphene-based coatings of variable thickness and crystallinity have been controlled by the alteration of the parameters of CVD processing, performed under CH4/H2 flux. Transmission electron microscopy has confirmed the effective growth of nanocrystalline graphene layers on the scaffolds due to the penetration of CVD gases into the open pores. The fully-connected and highly conductive 3D pathways have displayed a room temperature electrical conductivity in the range of 101–103 S m−1. Furthermore, the thermal conductivity has also increased by 50% for the specimen decorated with a 20 nm thick graphitic coating as compared to a bare 3D ceramic scaffold. The developed structures open up new possibilities for expanding the field of application of graphene/ceramic composites for conditions requiring dielectric substrates of various shapes coated with conductive films or graphene-based catalytic supports with good structural stability.