This paper presents the design and application of an environmental monitoring system on the historical site of Odda’s Chapel in Deerhurst, Gloucestershire, UK, and the determination of hygroscopic behaviour of the original building materials to obtain long-term moisture content variation. The monitoring system provides a comprehensive profile of hygrothermal conditions in the walls at the locations where moisture conditions are potentially causing decay and damage. The system makes use of temperature and relative humidity sensing technology placed on the wall construction, providing continuous data including rainfall, wind-driven rain and runoff rain measurements. The relative merits and results of the designed system are evaluated and discussed, as well as the implications of its application in the conservation of historical structures. The environmental monitoring results show general deterioration in the shell of the building. Internal wall surface measurements are essential for the documentation of wall interior response and should be conducted across the wall section at several locations. The fact that 91% of in-wall recorded relative humidity (RH) values are greater than 75% RH throughout the monitoring period demonstrates the need for measures to conserve this historical stone masonry.