In this paper, we studied the effect of the passivation of silicon nanowires (SiNWs) by silver nanoparticles (AgNPs) on the efficiency of Ag/SiNWs/Si Schottky diodes. SiNWs are obtained by one-step Ag-assisted chemical etching method. AgNPs were deposited on SiNWs using an electroless dipping method. Schottky junction devices have been successfully made using silicon nanowires coated with silver nanoparticles. The current–voltage (I-V) characteristics of Ag/AgNPs-SiNWs Schottky diode have been investigated by varying the immersion time in silver nitrate solution from 1 to 5 min. The I-V characteristics presented in logarithmic scale confirmed the domination of SCLC conduction mechanism at high voltage. The ideality factor (n), height of potential barrier (φb) and series resistance (Rs) of diodes are calculated by adopting the Cheung method. Compared to the Ag/SiNWs Schottky junction, the diode that presents AgNPs at the interface shows a significant improvement in electrical parameters. The potential barrier reaches 1.09 eV and the ideality factor is reduced to 2.64 with the presence of AgNPs for an immersion time of 1 min. Norde’s equation has also been used to calculate the series resistance and the potential barrier. The results obtained by Norde method are slightly shifted compared to those found by Cheung functions while the findings concerning the optimization of the immersion time are practically the same.