Graphene draws a lot of attention due to its exceptional electrical, mechanical, thermal, optical and chemical properties. However, its zero bandgap is a limitation for electronics applications and its two-dimensional (2D) nature is a limitation for large scale, volumetric and macroscopic applications. Doping graphene with heteroatoms and creating graphene hetero-structures are two approaches herewith suggested to sidestep the above limitations. The illustration of thus approaches begins with the chemical vapor deposition (CVD) growth of graphene in the form of either atomically thin films or 3D porous structures; which involves the synthesis of several structures such as nitrogen-doped graphene, graphene-carbon nanotube hybrids, in-plane graphene-boron nitride heterostructures, and graphene-molybdenum carbide hybrids. The analysis of impurities in CVD grown graphene at the atomic scale and the measurement of fracture toughness of graphene will then follow. Furthermore, the potential applications of as-synthesized materials like field emitters, supercapacitors, and catalysts for water splitting are discussed.