An amphiphilic perylenetetracarboxylic diimide derivative with four 4-tert-butylphenoxy substituents at the bay positions (named as TPDI) has been used as not only the functional organic materials but also the organic template for growth of CdS nanoparticles. The highly ordered TPDI/CdS hybrid film was obtained where the petals-like CdS nanocrystals with a uniform size (about 50 nm) grown on the surface of TPDI film successfully. The crystalline regions for CdS were identified to be hexagonal wurtzite. Examination by spectroscopic methods revealed TPDI molecules in both pure film and hybrid film all adopt a typical J-aggregation mode with a slight declining orientation angle with respect to the substrate from 24.8° to 21.9° after incorporation of CdS nanoparticles into the TPDI matrix. In particular, energy transfer from CdS to TPDI is established by both increased fluorescence emission intensity and fluorescence quantum yield of TPDI in the hybrid film. Furthermore, the enhanced conductivity and electron mobility are obtained for the hybrid film relative to those of the pure film based on current-voltage (I-V), field-effect transistor (FET) and photocurrent measurements. Unexpectedly, photo-induced electron-transfer from TPDI molecules to CdS nanocrystals is revealed through much more enhanced conductivity and electron mobility for the TPDI/CdS hybrid film relative to pure TPDI film upon 365 nm UV light irradiation. In only one TPDI/CdS hybrid system, the energy band alignment of TPDI and CdS nanoparticles makes evident possibility for electron transfer, while their electronic absorption and fluorescence emission features provide reasonability for both electron and energy transfer.