For years graphene has been considered as the most potential material which paves the way to advanced spintronic devices [1][2][3][4][5][6] due to its extraordinary electrical and physical properties. [7][8][9][10] The long spin diffusion length in graphene originated from the weak spin-orbit interaction and high electron mobility have stimulated numerous studies on developing graphene-based lateral spin valve (SV) in the past decade. [11][12][13][14][15][16] Apart from the application to lateral SV dealing with in-plane spin transport in a graphene channel, another potential application that is the implementation of graphene as a spacer material in vertical SV has recently become a subject of intense interest. [17][18][19][20][21][22] In development of vertical SV, the achievement of both the low resistance-area (RA) product and large magnetoresistance (MR) ratio is required for the realization of read heads for ultrahigh-density hard disk drives, [23] and magnetic random access memory [5,6] with high-speed operation and low power consumption. However, the current technology Graphene-based vertical spin valves (SVs) are expected to offer a large magnetoresistance effect without impairing the electrical conductivity, which can pave the way for the next generation of high-speed and low-power-consumption storage and memory technologies. However, the graphene-based vertical SV has failed to prove its competence due to the lack of a graphene/ferromagnet heterostructure, which can provide highly efficient spin transport. Herein, the synthesis and spin-dependent electronic properties of a novel heterostructure consisting of single-layer graphene (SLG) and a half-metallic Co 2 Fe(Ge 0.5 Ga 0.5 ) (CFGG) Heusler alloy ferromagnet are reported. The growth of high-quality SLG with complete coverage by ultrahigh-vacuum chemical vapor deposition on a magnetron-sputtered single-crystalline CFGG thin film is demonstrated. The quasi-free-standing nature of SLG and robust magnetism of CFGG at the SLG/ CFGG interface are revealed through depth-resolved X-ray magnetic circular dichroism spectroscopy. Density functional theory (DFT) calculation results indicate that the inherent electronic properties of SLG and CFGG such as the linear Dirac band and half-metallic band structure are preserved in the vicinity of the interface. These exciting findings suggest that the SLG/CFGG heterostructure possesses distinctive advantages over other reported graphene/ferromagnet heterostructures, for realizing effective transport of highly spin-polarized electrons in graphene-based vertical SV and other advanced spintronic devices.