The article presents the potential application of the time domain reflectometry (TDR) technique to measure moisture transport in unsaturated porous materials. The research of the capillary uptake phenomenon in a sample of autoclaved aerated concrete (AAC) was conducted using a TDR sensor with the modified construction for non-invasive testing. In the paper the basic principles of the TDR method as a technique applied in metrology, and its potential for measurement of moisture in porous materials, including soils and porous building materials are presented. The second part of the article presents the experiment of capillary rise process in the AAC sample. Application of the custom sensor required its individual calibration, thus a unique model of regression between the readouts of apparent permittivity of the tested material and its moisture was developed. During the experiment moisture content was monitored in the sample exposed to water influence. Monitoring was conducted using the modified TDR sensor. The process was additionally measured using the standard frequency domain (FD) capacitive sensor in order to compare the readouts with traditional techniques of moisture detection. The uncertainty for testing AAC moisture, was expressed as RMSE (0.013 cm3/cm3) and expanded uncertainty (0.01–0.02 cm3/cm3 depending on moisture) was established along with calibration of the applied sensor. The obtained values are comparable to, or even better than, the features of the traditional invasive sensors utilizing universal calibration models. Both, the TDR and capacitive (FD) sensor enabled monitoring of capillary uptake phenomenon progress. It was noticed that at the end of the experiment the TDR readouts were 4.4% underestimated and the FD readouts were overestimated for 12.6% comparing to the reference gravimetric evaluation.