Atomic functionality of two-dimensional (2D) materials, typically with a controllable doping route for offering regular atomic arrangement as well as excellent magnetism, is crucial for both fundamental studies and spintronic applications. Here, the adsorptions of the 5f-electron actinide series (An = Ac-Am) on porous graphene-like carbon-nitride (gh-C3N4) layers are explored to determine their structural stabilities, electronic nature and magnetic properties using the combination of density functional theory (DFT) calculations, ab initio molecular dynamics (AIMD), Monte Carlo (MC) simulations and chemical bonding analyses. Our investigations reveal that each An atom can be individually adsorbed at the vacancy site of gh-C3N4 sheet with high energetic, thermal and dynamical stabilities, which are rooted in the major interactions of ionic An-N bonding as well as the minor interactions of covalent bonding of An-5f6d states with N-2s2p states. The delocalization of a very few 5f electrons is dependent on whether they occupy the suborbitals that are matching and conducive to hybridize with the ligand orbitals forming the 5f-2s2p covalent bonds. We propose that the Ruderman-Kittel-Kasuya-Yosida (RKKY) mechanism plays a determining role for the inter-atomic 5f-5f magnetic exchange via the 6d electrons as the conduction electrons. Large magnetic moment and magnetic anisotropy energy (MAE) from the localized 5f electrons, together with the metallic characteristics owing to the delocalized 6d electrons, render these An-based 2D materials excellent metallic magnets, especially for the U@gh-C3N4 system with the modest magnetic moment of 0.6 μB, large MAE of 53 meV and high Curie temperature (TC) of 538 K.