Spinacia oleracea L. extract was immobilized on an octadecyl-bonded silica surface to produce a new sorbent for the solid-phase extraction of trace amounts of metal ions from aqueous neutral samples. A measurement of the metal content has been performed by using graphite furnace atomic absorption spectroscopy. The affinity of the investigated bivalent metal cations for the modified sorbent are in the order: Pb(II) > Cu(II) > Ni(II) > Zn(II) ≈ Cd(II) ≈ Co(II). The quantum-chemically calculated chlorophyll-a–metal ion binding energies were consistent with the measured affinities of the corresponding metal ions to the investigated sorbent. The maximum sorption capacity obtained for Pb(II) was equal to 1.44 μmol/g. The value of lead uptake was significantly higher in comparison to the one reported for other sorbents and biosorbents. Immobilized chlorophyll a is responsible for a chelation process with stoichiometry 1:1 owing to the porphyrin rings, which was confirmed by the quantitative analysis performed by reversed-phase high-performance liquid chromatography with diode array detection. The Toth adsorption isotherm model was applicable to the description of the adsorption process of either chlorophyll a or Pb(II). The structural analysis of sorbent was done using Fourier-transform Raman spectroscopy and scanning electron microscopy with an energy dispersive X-ray detector.