The crystal structure of Hellwinkel's salt [P(2,2'-biphenylyl)₂]⁺[P(2,2'-biphenylyl)₃]^- (1) is reported and the crystal packing analysed. The cation [P(2,2'-biphenylyl)₂]⁺ (P⁺) is analogous to Ph₄P⁺, and the anion [P(2,2'-biphenylyl)₃]^- (P^-) is analogous to [M(bipy)₃]^z complexes, both of which form multiple aryl embraces in crystals, but not previously with each other. The chirality of P- is potentially valuable for the resolution of chiral cations. The crystal supramolecularity of 1 is comprised of (1) a P^-...P^- sixfold aryl embrace with a calculated energy of 8.9 kcal mol^-1 attraction, (2) a tight homochiral embrace P⁺...P^- embrace using offset-face-to-face interactions between biphenylyl ligands (calculated attraction 21.0 kcal mol^-1), (3) a parallel fourfold aryl embrace P⁺...P⁺ (calculated attraction 1.2 kcal mol^-1), and (4) several non-standard P⁺...P^- embraces (calculated attractions 13.9, 18.3 kcal mol^-1). Comparisons with related crystals are made. The prognosis for application of P^- to the resolution of phenylated molecules and cationic metal complexes with phenylphosphonium or phenylarsonium ligands is good.