Hybrid materials formed by carbon fullerenes and layered materials have emerged due to their advantages for several technological applications, and phosphorene arises as a promising two-dimensional semiconductor for C60 adsorption. However, the properties of phosphorenefullerene hybrids remain mainly unexplored. In this work, we employed density functional theory to obtain structures, adsorption energies, electronic/optical properties, binding (AIM, NBO), and energy decomposition analyses (ALMO-EDA) of nanostructures formed by phosphorene and fullerenes (C24 to C70). We find fullerenes form covalent and non-covalent complexes with phosphorene depending on the molecular size, showing remarkable stability even in solution. Two classes of covalent complexes arise by cycloaddition-like reactions: the first class, where short-range effects (charge-transfer and polarization) determines the stability; and the second one, where short-range effects decay to avoid steric repulsion, and balanced longrange forces (electrostatics and dispersion) favors the stability. Otherwise, high-size fullerenes (C50 to C70) only form non-covalent complexes due to strong repulsion at shorter intermolecular distances and lack of dissociation barriers. In terms of electronic properties, fullerenes act as mild p-dopants for phosphorene, increasing its polar character and ability to acquire induced dipole moments (polarizability). Also, small energy-bandgap fullerenes (<0.8 eV) largely increase the phosphorene metallic character. We also note fullerenes retain their donor/acceptor properties upon adsorption, acting as active sites for orbital-controlled interactions and maximizing the phosphorene light absorbance at the UV-Vis region. Finally, we strongly believe our study will inspire future experimental/theoretical studies focused on phosphorene-fullerene uses for storage, anode materials, sensing, phosphorene bandgap engineering, and optoelectronics.<br>
