Four-dimensional printing (4DP) technologies are revolutionizing the fabrication of stimuli-responsive devices. To advance the analytical performance of conventional solid-phase extraction (SPE) devices using 4DP technology, in this study, we employed N-isopropylacrylamide (NIPAM)-incorporated photocurable resins and digital light processing three-dimensional printing to fabricate an SPE column with a [H+]/temperature dual-responsive monolithic packing stacked as interlacing cuboids to extract Mn, Co, Ni, Cu, Zn, Cd, and Pb ions. When these metal ions were eluted using 0.5% HNO3 solution as the eluent at a temperature below the lower critical solution temperature of polyNIPAM, the monolithic packing swelled owing to its hydrophilic/hydrophobic transition and electrostatic repulsion among the protonated units of polyNIPAM. These effects resulted in smaller interstitial volumes among these interlacing cuboids and improvements in the elution peak profiles of the metal ions, which, in turn, demonstrated the reduced method detection limits (MDLs; range, 0.2-7.2 ng L-1) during analysis using inductively coupled plasma mass spectrometry. We studied the effects of optimizing the elution peak profiles of the metal ions on the analytical performance of this method and validated its reliability and applicability by analyzing the metal ions in reference materials (CASS-4, SLRS-5, 1643f, and Seronorm Trace Elements Urine L-2) and performing spike analyses of seawater, groundwater, river water, and human urine samples. Our results suggest that this 4D-printed elution-peak-guided dual-responsive monolithic packing enables lower MDLs when packed in an SPE column to facilitate the analyses of the metal ions in complex real samples.