The influence of sodium thiosulfate (THS) concentration in Ag colloid/THS/H(2)TMPyP and Ag colloid/H2TMPyP/THS systems (H2TMPyP = 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin) was investigated by a combination of surface-enhanced resonance Raman scattering (SERRS) spectroscopy, surface plasmon extinction (SPE) measurements, and transmission electron microscopy (TEM). THS was found to have a strong impact on Ag nanoparticle surface structure and aggregation state and on interaction with H2TMPyP probe molecules, as evidenced by variations of the SERRS spectrum. In the Ag colloid/THS/H2TMPyP system, when laser-ablated Ag colloid was THS pretreated prior to the porphyrin addition, a critical threshold THS concentration (4 x 10(-5) M) was discovered. At concentrations below the threshold, THS mainly reduces the number of Ag+ adsorption sites. This leads to increased Ag nanoparticle aggregation prior to the porphyrin addition and significant weakening of the overall SERRS signal. Dominant contributions in the SERRS spectrum correspond to free base H2TMPyP and Ag+ containing the AgTMPyP form. At concentrations above the threshold, THS mediates also the formation and stabilization of new adsorption sites, probably Ag(0) sites. This induces a turn in the aggregation state of the pretreated Ag-c/THS system, an increase of the overall SERRS signal, and the appearance of a new spectral form of Ag metalated porphyrin.