Peptide-based nanomaterials are increasingly gaining popularity due to their specificity, biocompatibility, and biodegradability. In this work, a new multi-layered peptide-based biocomposite for targeting MCF-7 breast cancer cells is developed. The amphipathic Fluorenylmethyloxycarbonyl (Fmoc)-Leu-Ser peptide is synthesized, which is conjugated to a tumor-targeting peptide sequence Gly-Cys-Gly-Asn-Ser to form Fmoc-L-S-G-C-G-N-S (FLS) assemblies. To the FLS assemblies, gold nanorods are then attached to develop drug delivery vehicles (DDVs). The DDVs are entrapped with the anti-cancer drug fulvestrant. Entrapment efficiency is found to be 50.6%. Release studies indicate that irradiating the gold nanorod bound DDVs at NIR wavelength (785 nm) increases drug release by fourfold compared to assemblies that are not irradiated. These results also show higher cytotoxicity and lower cell invasion due to photo-triggered drug release. Furthermore, distinct actin cytoskeletal changes are observed. Such novel peptide-based gold nanorod bound DDVs demonstrate potential in dual targeting of MCF-7 breast cancer cells.