A series of azathia- and azaoxathiacrown ether macrocycles have been prepared in good yields via the use of N-boc-bis(2-chloroethyl)amine as a precursor, which minimises undesirable side reactions and facilitates subsequent deprotection to the free cyclic amine. The mono-aza macrocycles, [12]aneNS 3, [12]aneNOS 2, [15]aneNS 4, [15]aneNO 2S 2 and [16]aneNS 4 have been prepared via this route. The single-crystal X-ray structure of [12]aneNS 3 · HBr · 2H 2O confirms the macrocycle to be distorted quadrangular with the S-centres lying along the edges and six out of 12 torsion angles less than 90°. The synthesis of di-aza macrocycles utilising the diamide precursors, N, N′-bis(chloroacetyl)-1,2-diaminoethane and N, N′-bis(chloroacetyl)-1,3-diaminopropane, affords the free macrocycles [12]aneN 2S 2, [15]aneN 2S 3, [15]aneN 2OS 2, [16]aneN 2S 3 and [19]aneN 2S 4 after reduction of the intermediate cyclic amides. Reaction of 3,6-dioxa-1,8-octanediamine with the dimethyl ester of thiadiglycolic acid followed by reduction affords [15]aneN 2O 2S, while the hydroxy-substituted macrocycles [20]aneS 6(OH) 2, [13]aneS 4(OH), and [26]aneS 8(OH) 2 have been prepared by reaction of 1,3-dichloro-2-hydroxypropane with the appropriate dithiol. The crystal structure of [20]aneS 6(OH) 2 shows two endo- and four exo-dentate S-centres as observed in the parent [18]aneS 6. The N-aryl substituted macrocycles N-4-NO 2Ph-[12]aneNS 3 ( N-4-nitrophenyl-7-aza-1,4,10-trithiacyclododecane) and N-4-NH 2COPh-[12]aneNS 3 ( N-4-benzamido-7-aza-1,4,10-trithiacyclododecane) have been prepared by reaction of 4-substituted bis-tosylated N, N-bis(2-hydroxyethyl)aniline with 3-thia-1,5-pentanedithiol.