Dopamine (DA) is a vital biomarker for the early diagnosis of dopaminergic dysfunction; therefore, it is important to establish a direct and selective detection tool for DA neurotransmitters. This work reports facilely synthesized Au-Ag core-shell nanoparticles (Au@Ag NPs) as colorimetric sensing probes for highly selective detection of the DA neurotransmitter. Our sensing strategy is based on DA-mediated aggregation of the Au@Ag NPs, which can show a distinct color transition from yellow to greenish grey. With the increase of pH from 6 to 10, the response time of colorimetric transition was significantly reduced by a factor of 10 and the limit of detection (LOD) for DA by a spectroscopic device was estimated to be 0.08 μM. Notably, optimized sensing probes of Au@Ag NPs at pH 10 demonstrated an excellent selectivity to DA against various interfering components (including catecholamines (norepinephrine and epinephrine), lysine, glutamic acid, glucose, or metal ions). Our sensing system also exhibited the reliable detection of DA in spiked human serum with the relative standard deviation lower than 4.0%, suggesting its possible application to the direct detection of DA in biological fluids.