We fabricated an electrode chip with a structure coated by an insulation layer that contains dispersed SiO2 adsorbent particles modified by an amino-group on a source-drain electrode. Voltage changes caused by chelate molecule adsorption onto electrode surfaces and by specific cation interactions were investigated. The detection of specific cations without the presence of chelate molecules on the free electrode was also examined. By comparing both sets of results the complexation ability of the studied chelate molecules onto the electrode was evaluated. Five pairs of source-drain electrodes (x8 arrays) were fabricated on a glass substrate of 20 x 30 mm in size. The individual Au/Cr (1.0/0.1 mu m thickness) electrodes had widths of 50 mu m and an inter-electrode interval of 100 mu m. The fabricated source-drain electrodes were further coated with an insulation layer comprising a porous SiO2 particle modified amino-group to adsorb the chelate molecules. The electrode chip was equipped with a handy-type sensor signal analyzer that was mounted on an amplifier circuit using a Miniship (TM) or a system in a packaged LSI device. For electrode surfaces containing different adsorbed chelate molecules an increase in the sensor voltage depended on a combination of host-guest reactions and generally decreased in the following order: 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphine, tetrakis(p-toluenesulfonate) (TMPyP) as a Cu2+ chelator and Cu2+ > 2-nitroso-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (nitroso-PSAP) as an Fe2+ chelator and Fe2+ > 4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BPDSA) as an Fe2+ chelator and Fe2+ > 3-[3-(2,4-dimethylphenylcarbamoyl)-2- hydroxynaphthalene-1-yl-azo]-4-hydroxybenzenesulfonic acid, sodium salt (XB-1) as a Mg2+ chelator and Mg2+ > 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BCIDSA) as a Cu2+ chelator and Cu2+, respectively. In contrast, for the electrode surfaces with adsorbed O,O'-bis(2-aminoethyl)ethyleneglycol-N,N,N',N'-tetraacetic acid (GEDTA) or O, O'-bis(2-aminophenyl)ethyleneglycol-N,N,N',N'-tetraacetic acid, tetrapotassium salt, hydrate (BAPTA) as a Ca2+ chelator no increase in the detection voltage was found for all the electrode tests conducted in the presence of Ca2+. To determine the differences in electrode detection, molecular orbital (MO) calculations of the chelate molecules and surface molecular modeling of the adsorbents were carried out. In accordance with frontier orbital theory, the lowest unoccupied MO (LUMO) of the chelate molecules can accept two lone pair electrons at the highest occupied MO (HOMO) of the amino group on the model surface structure of the SiO2 particle. As a result, a good correlation was obtained between the LUMO-HOMO difference and the ion response of all the electrodes tested. Based on the results obtained, the order of adsorbed chelate molecules on adsorption particles reflects the different metal ion detection abilities of the electrode chips.