Two perylenediimide derivatives, N, N'-bis(3,7-dimethyloctyl)- 1,7-dicyanoperylene-3,4:9,10-tetracarboxyldiimide and N, N'- bis(3,7-dimethyloctyl)- 1,2,6,7-tetrachloroperylene-3,4:9,10-tetracarboxyldiimide, were prepared and their one-dimensional micro/nanorods were obtained in chloroform/methanol solution. The determination of sensing properties based on their conductometric gas sensors revealed that the increased current was one order of magnitude higher for core-tetrachlorinated perylene than that of core-cyanated one in hydrazine vapor (8 part per million). While better ambient stability in air was found for core-cyanated perylene due to its lower lowest unoccupied molecular orbital (LUMO) energy level and high-ordered arrangement in solid materials. The differential response to hydrazine vapor was less dependent on their surface area and morphologies. It should be ascribed to the difference in activation energy level and twisted skeleton, which are originated from chloride and cyano groups on the bay positions. Discussion for structure-function relationships suggest core-substituted groups have significant impact on the performance of perylene sensing device by modulating band gap and structure of skeleton. (C) 2014 Elsevier B.V. All rights reserved.