This article describes the synthesis of nanoporous silver submicrocubes (Np-Ag) capped with poly(allylamine hydrochloride) PAH/poly(styrenesulfonate) PSS bilayers (Np-Ag(PAH/PSS)(n), 1 <= n <= 4) via layer-by-layer (LBL) assembly for the electrochemical glucose sensing. The consecutive LBL encapsulation of Np-Ag (average size approximate to 530 nm) with positively charged PAH and negatively charged PSS layers was monitored by using zeta-potential analyses, which showed that the sign of the zeta-potential became positive (+10 mV) or negative (-22 mV) depending on the charge of the encapsulating species. The thickness of two PAH/PSS bilayers on the Np-Ag was estimated to be similar to 4 nm (consistent with a literature value of similar to 1 nm per PAH or PSS layer) on the basis of a high-resolution transmission electron microscopy image of the Np-Ag(PAH/PSS)(2). Moreover, the high quality of the polyelectrolyte capping on Np-Ag was evidenced by the elemental mapping analysis of particles (obtained by using high-angle annular dark-field scanning transmission electron microscopy), which showed a uniform spatial distribution of C, N, and S (derived from PAH and PSS layers). Among the four different Np-Ag(PAH/PSS)(n) (1 <= n <= 4) electrodes, Np-Ag(PAH/PSS)(2) exhibited the highest electrocatalytic activity toward glucose because of the optimal thickness and density of its polyelectrolyte films (fabricated onto Np-Ag). The (Np-Ag(PAH/PSS)(2) electrode demonstrated a detection limit of 20 mu M, a sensitivity limit of 472.15 mu A mM(-1) cm(-2), and a wide range of detection for glucose at concentrations as high as 23.3 mM along with good selectivity toward glucose. The findings of this study are expected to contribute to improvements in the fabrication and stability of various particle-type catalysts on an electrode surface and to efforts to optimize the device performance using the LBL encapsulation technique.