Silver nanoparticle aggregates were synthesized in large scale using resorcinol under alkaline condition to obtain an assembly of silver clusters. Stable dispersion of the cluster in aqueous medium has been examined out of resorcinol-capped silver nanoparticle assemblies. The UV-vis spectroscopy during the particle evolution has been studied in detail. From the high-resolution TEM (HRTEM) image and XRD pattern it was confirmed that the particles are made of pure silver only. The capping action of resorcinol has been authenticated from the FTIR spectra. UV-vis spectroscopy and TEM images reveal that the temperature, effect of vibrational energy, heat shock, and time-dependent particle evolution have unique bearing on the stability and surface properties of the clusters. The concentrations of silver nitrate, resorcinol, and NaOH have important influence on the particle evolution and its size. TEM images incite us to examine the aggregates to capitulate surface-enhanced Raman scattering (SERS) to the single molecular level using crystal violet (CV) and cresyl fast violet (CFV) as molecular probes. The SERS intensity of CV increases with increasing the size of the silver aggregate.