A practical and cheap methodology in modifying commercial coconut shell activated carbon for solid‐phase extraction of N‐nitrosodimethylamine in water was developed through an understanding of activated carbon surface chemistry. In comparison with commercial activated carbon, extraction recoveries by activated carbon treated with sulfuric acid decreased by 50%, while those of activated carbon heated at 800°C improved by more than 100%. Acid treatment increased the oxygen content on the carbon's surface. In contrast, heat treatment decreased the surface oxygen content, resulting in a more hydrophobic surface, which favoured adsorption and extraction of N‐nitrosodimethylamine. The influence of different activated carbon sizes, amount of modified activated carbon, and pH on the N‐nitrosodimethylamine recoveries was assessed and compared with the commercial solid‐phase extraction cartridge. The recommended amount of powder activated carbon treated at 800°C was 3 g to yield an optimum recovery of 130%, which was superior to the commercial solid‐phase extraction cartridges. The method validation results confirmed the high accuracy, reproducibility, and precision of the method. The study indicated that chemisorption plays a significant role in the adsorption of N‐nitrosodimethylamine on activated carbon, and the optimization of its surface chemistry can enhance N‐nitrosodimethylamine adsorption/extraction from water.