Au NRs protected with mPEG-SH molecules (mPEG-Au NRs) were demonstrated to be a promising platform for LSPR-based sensing of molecular biothiols in aqueous solution. Surface mPEG-SH molecules endow Au NRs with great stability and biocompatibility and no nonspecific adsorption of biomacromolecules. The LSPR band of mPEG-Au NRs displays a stability and linear response in the spectral shift with respect to;: change in their surrounding refractive index with a sensitivity of 252 nm/RIU. The loose structure of mPEG-SH around the Au NRs offers free sites, thereby allowing molecular biothiols to bind onto the surfaces of Au NRs. The LSPR response and the sensitivity of Au NRs to biothiols such as GSH, Cys, Hcy, TGA, GSSG, and BSA were then studied.