In this paper the combination of dispersive micro solid-phase extraction (DMSPE), using multiwalled carbon nanotubes (MWCNTs) as solid sorbents, with total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for preconcentration and determination of lead and cadmium ions in water samples. The proposed sample preparation is quite simple and economic. After the sorption processes of the metals on the MWCNTs, the aqueous sample is separated by centrifugation and the metal loaded MWCNTs are suspended using a small volume of an internal standard solution and analyzed directly by TXRF. Parameters affecting the extraction process (complexing agent, pH of the aqueous sample, amount of MWCNTs) and TXRF analysis (volume of the deposited suspension on the reflector, drying mode, and instrumental parameters) have been carefully evaluated to test the real capability of the developed methodology for the determination of Cd and Pb at trace levels. For both elements the linear range is observed up to 50 ng mL⁻¹. Under optimized conditions detection limits are 1.0 ng mL⁻¹ and 2.1 ng mL⁻¹ for Cd(II) and Pb(II) ions, respectively. Both of the examined elements can be determined with quantitative recoveries (ca. 100%) and with an adequate precision (RSD = 6.0% and 10.5% for Cd(II) and Pb(II), respectively). Our results give insight into the possibilities of the combination of DMSPE and TXRF for trace metal determination in different types of environmental waters (sea, river and waste water).