Reliable and ultrasensitive quantification of dopamine (DA) is essential in the precise diagnotherapy of neurological diseases. In this study, dual mode counterpropagating-responsive gold@silver nanoparticle-gold nanorod (Au@AgNP-AuNR) nano-assemblies were fabricated for the precise quantification of DA. The plasmonic Au@AgNP-AuNR assemblies possessed high surface-enhanced Raman scattering (SERS) activity and strong fluorescence quenching, due to the prominent electromagnetic enhancement between the hotspots of the assemblies. In the presence of a DA target, the Au@AgNP-AuNR assemblies dissociated, leading to an increase in fluorescence intensity and a decrease in SERS intensity. The limit of detection (LOD) of DA was 0.04 fM and 0.02 fM by the fluorescence method and SERS method, respectively. The linear range was 0.1-10 fM. These findings demonstrated that the simultaneous positive fluorescence response and negative SERS response ensured the accurate detection of DA, which opens up a new avenue for the early diagnotherapy of neurological diseases.