Copper (II) significantly enhanced tetracycline adsorption via acting as a bridge ion to form goethite–Cu2+–tetracycline complex because Cu2+ could form strong and specific inner-sphere surface complexes. Display omitted ► Background electrolyte cations showed almost no effect on tetracycline adsorption onto goethite. ► Copper (II) and humic acid enhanced the adsorption to different extent. ► Tetracycline was adsorbed by goethite through inner-sphere complextion. ► Copper (II) and humic acid have great effects on tetracycline mobility in soils. Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3–10. Five background electrolyte cations (Li+, Na+, K+, Ca2+, and Mg2+) with a concentration of 0.01M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu2+, could significantly enhance the adsorption and higher concentration of Cu2+, stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu2+ could enhance the adsorption via acting as a bridge ion to form goethite–Cu2+–tetracycline surface complex because Cu2+ could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.