Recently, graphene is of highly interest owing to its outstanding conductivity, mechanical strength, thermal stability, etc. Among various graphene synthesis methods, atmosphere pressure chemical vapor deposition (APCVD) is one of the best synthesis one due to very low diffusitivity coefficient and a critical step for graphene-based device fabrication. Hightemperature APCVD processes for thin film productions are being recognized in many diversity technologies such as solid-state electronic devices, in particular, high quality epitaxial semiconductor films for silicon bipolar and metal oxide semiconductor (MOS) transistors. Graphene-based devices exhibit high potential for applications in flexible electronics, optoelectronics, and energy harvesting. In this chapter, recent advances of APCVD-based graphene synthesis and their related applications will be addressed.