Low-field nuclear magnetic resonance (NMR) technology was used to perform the experiments of transverse relaxation time (T2), pore size distribution, and water absorption rate for wood-plastic composites (WPC) with different contents of added slag powder, exploring the water movement and the dynamic changes of pore size during the moisture absorption process of the material under immersion condition. The experimental results were as follows: (1) According to the T2 of H proton and its inversion pattern, the measured porosity had a relatively small difference from that of the weighing method. (2) The pore size distribution graph showed the following: (i) when the immersion time of composite materials was different, the changing law of volume of pores with different radius was different.; (ii) when the material’s immersion time was greater than 216 h, the pore radius and its distribution characteristics showed large differences; (iii) slag powder changed the pore structure of the WPC but did not change the water absorption characteristics of the wheat straw. (3) The changes of water absorption and expansion rate showed that the slag powder changed the time for the materials’ pores to absorb water until saturation and reduced the water absorption and expansion rate. The measurement results were consistent with changing trend in the pore size obtained by low-field NMR relaxometry.