There is still a lack of deep understanding on the reaction kinetics and mechanism of thiol etching of gold. Herein, by using the sensor of quartz crystal microbalance (QCM) as the sacrificial probe, the etching reaction of gold has been studied by employing cysteamine (CS) as a typical thiol etchant. The etching reaction is verified as diffusion-controlled and shows a half-order reaction kinetics. It is demonstrated that intact thiol and amino on CS are both crucial for its etching ability to gold. Applied potentials can affect the electron transfer and hence can be used to regulate the gold etching. Our results also reveal that only two carbon atoms of the spacer between thiol and amino on CS are very critical to the excellent etching ability. This work exhibits a new route to explore the thiol etching reaction of gold and elucidates the reaction kinetics and mechanism.