Optical motion capture systems are widely used in biomechanics although have not been significantly explored for measuring volumes and volume variations yet. The aim of this study was to propose and test a completely novel procedure for the calibration of motion capture systems for the breathing analysis in terms of volume measurements, by the use of a tool consisting in an ad-hoc designed in-situ calibration device (CD) and two algorithms for calibration. Both the calibration tool and the calibration procedure performed in the range 0-2780mL on an Optoelectronic Plethysmography (OEP) system are presented. The CD delivered known volume (ΔVCD) variations to the OEP; the two algorithms performed the calibration by the comparison between ΔVCD and OEP recorded volume (ΔVOEP), in both static and dynamic conditions. Discrimination threshold, accuracy, precision and repeatability for the volume variation measurements have been evaluated, as well as the calibration curve of the OEP. OEP volume threshold of ±8.92mL was assessed; the volume measurement accuracy was always better than 6.0% of measured volume, and a volume repeatability of ±2.7mL was found. Lastly, the calibration curve was assessed to be ΔVOEP= 0.962·ΔVCD. Results demonstrate that the proposed calibration procedure can be useful to provide an in-situ accurate calibration of motion capture systems in the volume analysis, to optimize the hardware and the software of the available system for volume measurement as well as to establish the motion capture system appropriateness, in terms of technical suitability and data quality.