Abstract Surface architectures based on gold nanoparticles (AuNPs) electrodeposited on gold ultramicroelectrode arrays (UMEAs) and further modified with self‐assembled monolayers (SAMs) of two different thiol molecules were evaluated. The voltammetric behavior of the resulting electrochemical transducer approaches appeared to be fairly different compared to that of SAM‐modified UMEAs and microelectrode counterparts. Such behavior indicates that the electrodeposited AuNPs played a key role in the arrangement of the thiolated probes and the electron transfer processes at the transducer solution interface. A detailed description of this phenomenon was carried out with the aim of showing the potential of the presented SAM‐AuNP‐UMEA based transducer to develop robust biosensor approaches.