We place fullerenes initially 5 Å away from the phosphorene surface; at least ten orientations for each molecule were considered according to its symmetry. The Phos-Fullerene systems form two groups of stable complexes depending on the fullerene size (Fig. In the case of the covalent complexes, the adsorption stability decreases as the size of fullerenes increases. C24, C26, and C34 form highly stable complexes, reaching positive adsorption energies of 2.1, 1.4, and 1.3 eV, respectively (favorable adsorption, Fig. ). Interestingly, Phos-C24 and Phos-C26 complexes form a [4+4]-cycloaddition bonding, which compares to prototype graphene-fullerene hybrids called graphene nanobuds, where covalently bonded fullerenes or fusing fragmented C60 are designed onto a graphene monolayer via cycloaddition reactions . Otherwise, C36, C40, and C44 reach relative medium stability upon adsorption, with positive adsorption energies of up to 0.9 eV (favorable adsorption). Structurally, C34, C36, C40, and C44 fuse to phosphorene through cycloaddition of up [2+2] order, and adsorption energy decreases up to 67% compared to Phos-C24 and Phos-C26.