The treatment of combined antibiotics and heavy metals pollution is a critical challenge. Herein, iron and nitrogen co-doped biochar (Fe/N-BC) was synthesized using rape straw as precursor, and applied for the adsorption of ciprofloxacin (CIP) and Cu2+ in single and binary systems. The qmax for CIP and Cu2+ were 46.45 mg g−1 and 30.77 mg g−1, respectively. Adsorption decreased in a binary matrix, indicating that there was a competitive effect between CIP and Cu2+, which might be due to CIP and Cu2+ sharing similar active adsorption sites on Fe/N-BC. Interestingly, CIP and Cu2+ co-adsorption was a pH-dependent process. Fe/N-BC has potential to highly selectively separate CIP/Cu2+ from mixed solutions through adjusting pH values. Furthermore, adsorption mechanisms were systematically investigated in this research. This research could help to provide a deeper understanding of the synchronously removing specific antibiotics and heavy metals by biochar adsorbents.