In this contribution, four perylenediimide derivatives (PTCDIs) with different lengths and branched point of alkyl chain on bay region were prepared in order to probe the effect of alkyl chains on sensing performance. Studies on their sensing properties in hydrazine vapor revealed that about 4 orders of the magnitude in increased current was achieved for TPSA. This value is ca. 2, 2 and 23 times higher than that of DMB, TMSA and TESA, respectively. The differential response to the hydrazine vapor for these 10 PTCDIs gas sensors is less dependent of their surface area and morphologies. A well-ordered layer structure with smaller interplanar spacing allows TPSA possessing highly efficient sensing performance. A similar face-face packing mode and torsional angle of DMB and TMSA lead to both of them exhibiting almost same sensing performance in spite of the differences in interplanar spacing. While a greater torsional angle and head-to-tail aggregated modes with a greater interplanar spacing induce the less 15 efficient sensing performance of TESA sensors. This study indicates the length and branched point of alkyl silane on bay region have significant impact on performance of PTCDIs gas sensing devices by modulating torsional angle, interplanar spacing and stacking modes. 75