The functioning of an amperometric electrochemical sensor having an electrochemical cell is monitored by the electrochemical cell. A perturbation quantity is imposed on the sensor, which is operated with voltage control at a given polarization voltage. The response to the perturbation is measured and a check value is calculated, using the response under the perturbation as an input value. The check value is compared to a system-dependent limit value. If the check value is larger than the system-dependent limit value, the initial polarization voltage is changed by a predefined voltage increment and the process is repeated, until an optimal polarization voltage has been found, i.e., until the calculated check value is smaller than the system-dependent limit value. A measuring system that serves to carry out the method is also described. An automated embodiment utilizes a computer-supported control- and processing-unit with a data memory and a data-evaluating program.