Using THPC as the initial substrate, 2,6,7-trioxa-1,4-diphospha-bicyclo[2.2.2]-octane was gotten in strong basic environment by an indirect way. And then, after a series of reaction, the target Caged-diphospha-bicyclo compounds were synthesized using a new method. The whole procedure was reported in detail. Furthermore, the molecule structures and some spectra of the target compounds were also systematically described in this paper. Some valuable phenomena were discovered in ~13 P NMR spectra, such as the chemical shift from 2 to 5a and 5b, and the increase of ~3J P_P from 2 to 5 Using THPC as the initial substrate, 2,6,7-trioxa-1,4-diphospha-bicyclo [2.2.2] -octane was gotten in strong basic environment by an indirect way. And then, after a series of reaction, the target Caged-diphospha-bicyclo compounds were synthesized using a new method. The whole procedure was reported in detail. P NMR spectra, such as the chemical shift from 2 to 5a and 5b, and the increase of ~ 3J P_P from 2 to 5