In this paper, we are relating a significant improvement of the SERS effect achieved with assembled Au/ZnO nano-urchins. This improvement is realized thanks to an excellent capacity of adsorption (denoted K) for thiram molecules on these plasmonic nano-urchins, which is a key point to be taken into account for obtaining a SERS spectrum. Moreover, this outlook may be employed for different types of plasmonic substrates and for a wide number of molecules. We studied the capacity of the assembled Au/ZnO nano-urchins to be sensitive to the pesticide thiram, which adsorbs well on metals via the metal–sulfur bond. For the thiram detection, we found a limit concentration of 10 pM, a value of this capacity of adsorption (K) of 9.5 × 106 M−1 and a factor of analytical enhancement equal to 1.9 × 108.