This study now explores the potential for chemical functionalization of BPN using cyclooctyne (COC), the smallest, bottleable, cyclic alkyne with a highly strained triple bond (Scheme 1). Due to the reactivity and size of the molecule, it is used as a building block in organic synthesis and for the functionalization of semiconductor surfaces, providing the possibility to form wellordered patterns. Even a complete organic-inorganic interface consisting of up to 11 layers on Si(001) has been realized recently. Using density functional theory (DFT), we provide detailed insights into the thermodynamic properties and reaction barriers of the chemisorption of cyclooctyne, the theoretical maximum coverage, and the impact of covalent functionalization on the electronic structure. The regioselectivity of the adsorption is discussed as a prerequisite for ordered layers. We show that the formation of a well-ordered layer should be achievable, with the goal of a full covalent functionalization of the biphenylene network. This opens the road towards interfaces of this 2D material and organic layered structures.