The interaction and reaction of PCl3 and PCl3-H2S mixtures with the microporous materials Silicalite, ALPO-5, NaY, NaX, and NaA have been investigated, with the intention of producing phosphorus sulfide clusters in the pores. A rich chemistry was observed and monitored by solid state 31P NMR. The presence of P4S3, α-P4S5, β-P4S6, and P4S7 inside the NaY α-cages was demonstrated, as well as a new species that is possibly a third geometric isomer of P4S4 with C3v symmetry. 129Xe NMR showed the exclusion of Xe from the micropores by the phosphorus sulfides. Sulfides lower than P4S7 are small enough that they undergo rapid pseudo-isotropic reorientation inside the NaY α-cage. Key words: phosphorus sulfides, intrazeolitic cluster synthesis.