In this study, an ultrasensitive unlabeled electrochemical immunosensor for the detection of cardiac troponin I (cTnI) was developed based on Pt/Au modified B,S,N co-doped reduced graphene oxide (Pt/Au-B,S,N-rGO) as a signal amplification platform. First-principles calculations were employed to analyze the electron density of states of Pt/Au-B,S,N-rGO, revealing an increase in the electron density of the graphene oxide (GO) states. Furthermore, scanning electron microscopy (SEM), X-ray photoelectron diffraction spectroscopy (XPS), and electrochemical detection were used to successfully construct and analyze Pt/Au-B,S,N-rGO. The results showed that B,S,N-rGO exhibited good electrochemical activity, and the Au/Pt NPs demonstrated excellent catalytic properties, which provided a strong foundation for achieving high-sensitivity detection. Moreover, the constructed unlabeled electrochemical immunosensor had an ideal linear range (0.1 pg/mL similar to 50 ng/mL) and detection limit (0.082 pg/mL). In human serum detection, the results of this immunosensor were essentially similar to the ELISA results for the same samples, which suggested that the immunosensor had a promising clinical application prospect for the detection of cTnI.