As a zero-band semiconductor, graphene is an attractive material for a wide variety of applications such as optoelectronics. Among various techniques developed for graphene synthesis, chemical vapor deposition (CVD) on copper foils shows high potential for producing few-layer and large-area graphene. Since fabrication of high-quality graphene sheets requires the understanding of growth mechanisms, and methods of characterization and control of grain size of graphene flakes, analytical modeling of graphene growth process is therefore essential to controlled fabrication. The graphene growth process starts with randomly nucleated islands that gradually develop into complex shapes, grow in size, and eventually connect together to cover the copper foil. To model this complex process, this chapter introduces a physical–statistical approach under the assumption of self-similarity during graphene growth. The growth kinetics is uncovered by separating island shapes from area growth rate.