Charge-transfer complexes 2([15]aneS₅)·7I₂ 1 ([15]aneS₅ = 1,4,7,10,13-pentathiacyclopentadecane), [18]aneS₆·I₂ 2, [18]aneS₆·4I₂ 3 ([18]aneS₆ = 1,4,7,10,13,16-hexathiacyclooctadecane), [24]aneS₈·I₂ 4 and [24]aneS₈·6I₂ 5 ([24]aneS₈ = 1,4,7,10,13,16,19,22-octathiacyclotetracosane) have been prepared and their structures and solution properties investigated. The compounds were prepared by slow evaporation of solutions containing I₂ and the appropriate thioether macrocycle in CH₂Cl₂. The single-crystal structure determination of 1 shows three I₂ molecules co-ordinated to three exo oriented S donors [S(1)–I(1) 2.797(3), I(1)–I(1′) 2.798(2), S(4)–I(4) 2.885(4), I(4)–I(4′) 2.764(2), S(7)–I(7) 2.828(3) and I(7)–I(7′) 2.779(2) Å; S(1)–I(1)–I(1′) 178.39(8), S(4)–I(4)–I(4′) 171.12(8), S(7)–I(7)–I(7′) 178.80(8)°]. The fourth I₂ molecule (with a site occupancy of 0.5) lies close to S(10) [I(10)–S(10) 2.839(5) Å], the bond distance I(10)–I(10′) 2.674(3) Å being unusually short. Compound 2 is an example of a 1∶1 I₂∶macrocycle adduct and shows symmetrically bridging I₂ molecules [S(1)–I(1) 3.099(2), I(1)–I(1ⁱ) 2.7881(10) Å; S(1)–I(1)–I(1ⁱ) 178.68(4)°; i 1 – x, 1 – y, 1 – z] between [18]aneS₆ macrocycles. Compound 3 is the first example of an adduct between I₂ and a homoleptic thioether macrocycle which shows both exo [S(1)–I(1) 2.838(2), I(1)–I(1′) 2.7875(6) Å; S(1)–I(1)–I(1′) 174.95(4)°] and endo [S(4)–I(4) 2.792(2), I(4)–I(4′) 2.8067(7) Å; S(4)–I(4)–I(4′) 174.43(4)°] co-ordination of I₂ molecules. The endo-oriented I₂ molecules occupy space above and below the macrocyclic plane with the macrocycle adopting a sigmoid conformation. The single-crystal structure determination of the 1∶1 adduct 4 shows symmetrically bridging I₂ molecules [S(1)–I(1) 3.215(2) and I(1)–I(1ⁱ) 2.758(2) Å; S(1)–I(1)–I(1ⁱ) 172.75(3)°; i –x, –y, –z] which are a characteristic of this stoichiometry. Compound 5 contains endo- and exo-oriented S donors within the same adduct [I(1)–I(1′) 2.7861(8), I(4)–I(4′) 2.7937(8), I(7)–I(7′) 2.8345(8), S(1)–I(1) 2.821(2), S(4)–I(4) 2.815(2), S(7)–I(7) 2.741(2) Å; S(1)–I(1)–I(1′) 170.15(5), S(4)–I(4)–I(4′) 177.41(5), S(7)–I(7)–I(7′) 177.24(5)°]. These results are discussed in the context of the stability and characteristics of thioether crown–iodine charge-transfer complexes, and a qualitative MO diagram is proposed to account for the shorter I–I distances in bridging I₂ fragments compared to those in terminally bound I₂.