In this article, we report the synthesis of silver nanospheres (Ag NS) by a simple microwave irradiation method using Triton X 100 (TX 100) as a capping agent. TX 100 was also observed to act as a reducing agent in the presence of microwave radiation. From the ultraviolet-visible spectrum, the formation of Ag NS was confirmed by observing surface plasmon resonance band at 414 nm. The emission band of Ag NS was observed at 482 nm from the photoluminescence (PL) spectrum. High-resolution transmission electron microscopy (HR TEM) was used to investigate the morphology of the synthesized sample. It shows that the synthesized sample has sphere-like morphology with an average diameter of 5 nm. Further, the elemental composition of the Ag NS was determined by energy dispersive x-ray analysis (EDX). Selected area electron diffraction (SAED) was used to find the crystalline nature of the Ag NS. The interaction between Ag NS and TX 100 was established by Raman spectroscopy. The electrochemical behaviour of the synthesized Ag NS was analyzed by cyclic voltammetry (CV). © 2013 Copyright Taylor and Francis Group, LLC.