A fast and simple dispersive solid-phase microextraction method (d-SPμE) was described for the determination of copper and lead in food, water, and sediments using FAAS. Firstly, nanoflower Al2O3@carbon spheres composite (NF Al2O3@CSs) was synthesized and then characterized. The obtained NF Al2O3@CSs was used for the d-SPμE of copper and lead in aqueous solutions. The influence of important parameters like pH, contact time, eluent conditions, volume of sample, and competing ion effects on the d-SPμE efficiency of copper and lead was investigated. They were pH, 7; eluent, 2 mol L−1 HCl (2 mL); sample volume, 250 mL for copper and 150 mL for lead with recoveries ≥90%. The adsorption and elution of analytes on NF Al2O3@CSs were realized quickly without vortexing. The LODs of the d-SPμE for copper and lead were found to be 0.69 μg L−1 and 2.8 μg L−1, respectively, while its PF was 125 for copper and 75 for lead. The intra-day precision and inter-day repeatability (RSD%, n = 7) were 1.3% and 1.6% for Cu(ii) and 2.3% and 3.2% for Pb(ii), respectively. Finally, the accuracy of the d-SPμE was investigated by determination of the analytes in four certified reference materials (TMDA-53.3 Lake water, NW-TMDA-54.6 Lake water, NIST 1573a Tomato leaves, and NIST RM 8704 Buffalo River Sediment). The analyte recoveries together with analyses of dam water, river water, wastewater, sea water, sumac, tea, chocolate, and lentils were studied. The results indicate that recoveries ranged from 90 to 103% in water samples and 91 to 110% in food samples.