Pyrogallol is anchored onto cellulose via -NH-CH2-CH2-NH-SO2-C6H4-N=N-linker to prepare an effective sorbent for solid-phase extraction of Cu(II), Zn(II), Fe(III), Ni(II), Co(II), Cd(II), and Pb(II) from aqueous solutions. The modified cellulose is characterized by FT-IR, C-13 CPMAS NMR, TGA, and elemental analyses. The conditions for effective sorption are optimized with respect to different experimental parameters in both batch and column processes. The feasibility of the sorption process was judged from both kinetic and thermodynamic points of view. The lower limit of detection as well as the enrichment factor for each metal ion was evaluated. Analytical utility of the solid-phase extraction is illustrated by successful determination of metal ions in natural water, pharmaceutical, and milk samples by flame AAS coupled with enrichment on cellulose loaded with pyrogallol.