A multisensor with a four-sectional membrane based on two Li- and two K-ionophores with different selectivities has been developed based on the laser-scanned silicon transducer (LSST), where the responses of the sensor sections have been measured by scanning the potentials at different points on the membrane surface. An artificial neural network (ANN) was employed for the analysis of mixed solutions. It has been demonstrated that by applying this hybrid sensor as a laser-scanned multisensor system, the concentration regions for the simultaneous determination of lithium and potassium ions in complex solutions have been enlarged significantly. It has been shown that using such a kind of multisensor system makes it possible to overcome the restriction of the selectivity in comparison with single sensors.