Silica two-dimensional substrates and nanowires (NWs) forests have been successfully decorated with Au nanoparticles (NPs) through laser ablation by using a pulsed ArF excimer laser, for sensor applications. A uniform coverage of both substrate surfaces with NPs has been achieved controlling the number of laser pulses. The annealing of the as-deposited particles resulted in a uniform well-defined distribution of spherical NPs with an increased average diameter up to 25 nm. The deposited samples on silica NWs forest present a very good plasmonic resonance which resulted to be very sensitive to the changes of the environment (ethanol/water solutions with increasing concentration of ethanol) allowing the detection of changes on the second decimal digit of the refractive index, demonstrating its potentiality for further biosensing functionalities.