Cadmium (Cd) is one dangerous and widespread heavy metal that of great environmental concern. To cost-efficiently adsorb aqueous Cd under influence of various factors, this study succeeded in fabricating goethite-modified biochar (GBC) derived from distillers’ grains (DGs) for Cd sorption of different concentrations (10–100 mg L−1) at pH of 3, 6 and 8 with and without microcystin-LR (MC-LR). Sorption kinetics and isotherms data revealed that Cd sorption capacity of GBC and unmodified BC increased as pH elevated from 3 to 6 but stabilized when pH further elevated to 8. Pseudo-second-order and Langmuir models more accurately fitted to sorption data for both BCs, implying monolayer chemisorption of Cd onto BCs. GBC exhibited more robust sorption for each Cd concentration than unmodified BC, with the maximum sorption capacity of around 28 mg g−1 at neutral and weak alkaline pH. Notably, goethite-modification obviously increased bulk polarity, specific surface area, porosity and surface oxygenic group abundance of BC, thus strongly enhancing Cd sorption by creating more sorption sites mainly via pore-filling, electrostatic attraction, and also via complexation and cation exchange. Co-existing MC-LR of 100 μg L−1 did not obviously affect Cd sorption by both BCs for most Cd levels at each pH, mostly because sorption mechanisms diverged between MC-LR and Cd to largely avoid their competition for sorption sties. Thus, goethite could modify DG-BC as promising and cost-efficient sorbent for Cd even with co-existing MC-LR, especially at neutral and weak alkaline pH that common in the nature. This study was greatly implicated in modifying and applying DG-BC for Cd immobilization in MC-LR laden waters with various pH circumstances.