Optimization of extraction and enrichment parameters of chemical warfare agents and their related chemicals from water are presented using multiwalled carbon nanotubes (MWCNTs) as solid‐phase extractant. Selected analytes were O,O'‐dialkyl alkylphosphonates, nerve agent and mustards. Extraction parameters, including sample volume, nature and volume of washing and eluting solvent, were optimized. Recoveries of analytes were determined by GC–MS and ranged from 81 to 104%. A comparison with C18, hydrophilic–lipophilic balance and active carbon sorbents demonstrated the superiority of MWCNTs for non‐toxic analogues of nerve agents. Optimized conditions involve 40 mg MWCNTs as the sorbent, 5.0 mL water as the washing solvent, 3 mL ethyl acetate as the eluent and sample loading of 10 mL water spiked at 0.1 μg/mL. The limits of detection (LOD) were achieved down to 1 and 0.05 ng/mL in full scan and selected ion‐monitoring modes, respectively.