A new cholesterol organogelator 4 was synthesized and its gelation property was evaluated. It was confirmed that 4 was an effective gelator for various organic solvents and could self-assemble into network fibers with a bilayer of folded conformation in some organic solvents. Moreover, organogelator 4 could act as a template for the synthesis of novel pearl-necklace porous CdS nanofibers. The transcription process of organogel fibers into CdS nanofibers was investigated, and it was found that Cd2+ ions were coated on the organogel fibers by the interaction with ester groups of 4, which might lead to the change of the arrangement of the organogelator and seemed to serve as nucleation sites for metalization. The further growth of CdS began with these nucleation sites along the organogel fibers. Meanwhile, parts of 4 free from organogel fibers have an effect on the formation of the CdS nanofibers consisting of the network and wormlike CdS particles.