Examples for programmed self-assembly of a,b-unsatd. ketoximes carrying a terminal pyridine subunit are described. The oximes I [R1 = 3-MeC6H4, 4-MeOC6H4, Me, R2 = Me; R1 = Ph, R2 = Bu, Ph] were prepd. from 4-formylpyridine and R1CH2COR2, followed by oximation. Their solid-state structures were investigated by X-ray structural anal.; this demonstrated that I [R1 = 3-MeC6H4, R2 = Me; R1 = R2 = Ph] predictably form discrete cyclic aggregates stabilized by a network of hydrogen bonds and arom. interactions.