A solid-phase nanoextraction method has been developed for the extraction and preconcentration of polychlorinated biphenyls using carboxyl multiwalled carbon nanotubes as a solid nano-sorbent. Parameters affecting extraction efficiency such as sorbent amount, desorption solvent type and volume, extraction time, pH, and salt content have been studied. Under optimized conditions, the correlation coefficient was up to 0.9989, the limits of detection was in the range of 1.4-3.5 ng/L, and limits of quantification was between 4.8 and 11.6 ng/L. The recoveries were in the range of 99-106% for different spiked analytes. The relative standard deviation for water samples spiked with two different spiking levels has been between 4 and 10%. The proposed sustainable method is rapid, easy to use, and small consumption of organic solvent for the detection and determination of trace levels of polychlorinated biphenyls in environmental waters.