The title compound, (C30H25NPS)2[Pd2Br6] or (Ph3PNSPh2)2[Pd2Br6], was crystallized from the reaction of (Ph3PNSPh2)[BPh4] with (PPh4)2[Pd2Br6], giving a salt rather than the intended coordination complex [PdBr3(Ph3PNSPh2)]. The compound crystallizes in the non-centrosymmetric space group Cc with one complete formula unit in the asymmetric unit. One of the two independent cations is disordered. The geometry of the two cations is compared with that of the only previously crystallized example of this cation, viz. its [SbCl6]- salt [Reck et al. (1982). Chem. Ber. 115, 2981-2996]. The bond angles within the P-N-S triad in the two cations in the title compound are narrower than those observed in the literature example, while the S-N bond lengths are slightly longer in the title compound. The P-N bond length in the ordered cation shows excellent agreement with that determined by Reck and co-workers, but the P-N bond lengths are lengthened slightly in the disordered cation. Weak C-H...Br interactions create a three-dimensional network, with cations and anions alternating along the crystallographic c direction.