The development of inexpensive and environmentally friendly graphene-like carbon is critical for its integration into industrial products. This work highlights the production of graphene-like carbon structures from calcium hydroxide. The chemical vapor deposition conditions to grow graphitic carbon on a calcium hydroxide catalyst are reported. Acetylene, steam, and calcium hydroxide are used to grow a crumpled carbon morphology. The crumpled carbon resulted in a high surface area of 1276 m2/g and high electrical conductivity (>105 S/m). Additionally, the significance and origin of the C 1s X-ray photoelectron spectroscopy (XPS) π-π* plasmon loss peak as it is related to high electrical conductivity is reported. A unique mechanism for the catalytic process involving calcium acetylide is proposed. Several deposition times, steam concentration, and catalyst morphology were tested to synthesize a variety of carbon morphologies from calcium-based materials. Crumpled carbon, hollow nanospheres, bamboo-like carbon nanotubes, multi-walled carbon nanotubes, and graphene fiber morphologies were all formed using calcium-based catalysts. Multiple reaction conditions, a scaled reaction (300 g), and catalyst recyclability were investigated. Calcium-based materials were then used as catalysts for the growth of other graphene-like carbons.