In this work, a simple, rapid and sensitive UV-visible spectrophotometric technique for the determination of copper based on injection-ultrasound-assisted dispersive liquid–liquid microextraction (IUSA-DLLME) was developed, using sodium diethyl-dithiocarbamate (Na-DDTC) as a complexing agent. The fabrication of a home-made microporous plastic tip was first reported, and by using it, contamination from a metallic tip was avoided; moreover cloudy solutions were easily obtained. Several parameters were investigated including the extraction solvent type and volume, pH of the reaction solution, concentration of DDTC, salt addition, reaction time and temperature, and sonication and centrifugation time. The results showed that carbon tetrachloride was a better extraction solvent. Under the optimal conditions, the calibration curve was linear in the range of 0.5–50 ng mL−1 of copper with a R2 of 0.9996. The relative standard deviation (RSD) for the determination of 0.5 ng mL−1copper was ±3.3% (n = 7), and the detection limit (3*Sb*c/m) was 0.05 ng mL−1 in the original solution. An enrichment factor of 222 was obtained. The developed method was validated by analysis of a certified reference solution and applied successfully to the determination of copper in tap water, bottled pure water and river water. The advantages of the IUSA-DLLME method are simplicity of operation, rapidity, low cost, low LOD and high enrichment factor.