Carbon nanomaterials, such as carbon nanoonions (CNOs), possess promising applications in various fields. There are urgent demands to synthesize carbon nanomaterials from a green and renewable carbon source. In this study, solid CNOs with relatively uniform size distribution (with diameters of about 30–50 nm), abundant structure defects and oxygen-containing surface functional groups (such as –OH and –COOH) are developed from co-pyrolysis of lignin (LG) and polyethylene (PE) in the presence of Ni-based catalysts. The type of catalyst, the concentration of catalyst and catalytic co-pyrolysis temperature play important roles in the morphologies and properties of CNOs as confirmed by TEM and SEM. Furthermore, the produced CNOs can act as a low-cost and highly-efficient adsorbent to remove Cu(II) from aqueous solution according to a homogeneous monolayer, chemical action-dominated, endothermic and spontaneous process. The theoretical maximum adsorption capacity of CNOs calculated from the Langmuir model is 100.00 mg g⁻¹. Surface deposition, complexation, π electron–cation interaction and electrostatic interaction are responsible for the adsorption of Cu(II) using the prepared CNOs.