A systematic study is conducted on the fluorination-enriched essential properties of two-dimensional (2D) graphene and onedimensional (1D) graphene nanoribbons using the first-principles method. The combined effects, which arise from the significant chemical bonds in C–C, F–C, and F–F bonds, the finite-size quantum confinement, and the edge structure, can greatly diversify geometric structures, electronic properties, and magnetic configurations. By the detailed analyses, the critical orbital hybridizations in determining the essential properties are accurately identified from the atom-dominated energy bands, the spatial charge distributions, and the orbital-projected density of states.