31P nuclei are used as probes in the NMR studies of xLi2O·P2O5·yCdO glass samples with different molar ratio (x, y). The static NMR spectra are obtained through employing the Bruker MSL-300 spectrometer with a operating frequency of 121.487 MHz. Three basic types of phosphorous structure units join together randomly to form networks in the glasses, each of which has its own NMR characteristic. The relative portions of those basic structure units depend on the molar contents of Li2O and CdO, i,e x and y. For the description of the unit portions, we have postulated a simple model, the rationality of which has been justified by the coincidence between the theoretical prediction based on the model and the conclusions obtained from the simulation of the observed NMR powder patterns.