The present invention provides a measurement device facilitating accurate quantitation of a substrate from a trace amount of sample and a highly reliable quantitating method of a substrate. The method uses an analysis element comprising a pair of electrodes for electrochemically quantitating reaction between a substrate in a sample and an oxidoreductase. One of the electrodes of the analysis element is a membrane formed on an inner wall of a cylindrical hollow space having an opening and the other is a needle. The needle electrode is projected temporarily external to the hollow space to puncture a subject and the resultant sample is collected from the subject.