Two highly sensitive and selective methods based on fluorescence (FL) and chemiluminescence (CL) emissions of 8-mercaptoquinoline-capped CdS quantum dots (MCQ-CdS QDs) were described for the determination of copper (II) after it’s preconcentration. High fluorescent CdS QDs, synthesized in an aqueous medium, generated a relatively intense CL emission in the presence of potassium permanganate as an oxidant. Furthermore, low quantities of copper (II) ions showed a remarkable quenching effect on both of the CL and FL emissions of MCQ-CdS QDs. Based on this effect, two selective and simple methods were established for Cu2+, and the detection limits of 0.28 and 0.026 ng mL−1 were obtained for the FL and CL methods, respectively. Also, due to the high propensity of MCQ to Cu2+, good selectivity was obtained and no sensible interfering effects from other metal ions were observed. To more sensitize the developed method, an efficient preconcentration process was designed based on the high-yield ultrasound-assisted temperature-controlled ionic liquid dispersive liquid–liquid microextraction (UA-TIL-DLLME) method. Under the optimum conditions, the extracted Cu2+ showed a suppressing effect on the FL and CL emissions of CdS QDs proportional to its initial concentration over the ranges of 0.008–1.4 and 0.001–1.4 ng mL−1, respectively. The limits of detection of 3.7 and 0.37 pg mL−1, respectively, were also achieved. The established methods showed great features and were satisfactorily applied to the monitoring of ultratrace Cu2+ in some different environmental samples.