The rapid identification of living cancer cells is highly crucial for cancer diagnosis, prognosis, and treatment monitoring. However, it is a great challenge to develop an effective way for rapid identification and imaging of cancer cells in a living state. Moreover, synthesis of monodisperse nanoparticles (NPs) with high sensitive surface-enhanced Raman scattering (SERS) activity is also a tough work. Herein, we creatively reported a convenient method to synthesize the novel NPs as the substrate of SERS sensors, which possessed a gold nanobipyramid core and silver nanorod shell. These gold nanobipyramid core and silver nanorod shell NPs (Au NBP@Ag NRs) were further modified with 4-mercaptobenzoicacid (4-MBA, Raman reporter molecule) and then conjugated with reduced bovine serum albumin (rBSA) and folic acid (FA) on their surfaces, to finally acquire Au NBP@Ag NR-MBA-rBSA-FA nanoprobes. In this system, With the enhancement factor (EF) of Au NBP@Ag NRs was about 4 × 10, it could significantly enhance Raman signal for Raman reporter molecules, and 4-MBA molecules performed high SERS signals based on their structures; the nanoprobes have favorable specificity and biocompatibility owing to the modification of rBSA which effectively avoided the nonspecific attachment of non-targeted cells. Moreover, the obtained SERS nanoprobes have excellent sensitivity for gastric cancer cells (MGC-803 cells) due to the conjugation of folic acid. Thus, the finally obtained Au NBP@Ag NR-MBA-rBSA-FA nanoprobes possess excellent detection efficiency for living MGC-803 cells. Therefore, our synthesized nanoprobes exhibit ultrasensitive SERS-activity, excellent specificity and superior cancer cells targeting ability, which could be applied for rapid identification and Raman imaging of living cancer cells via the SERS signal detection of the nanoprobes.