The purpose of this chapter is to examine the functional relationships between three types of risk (performance, financial and psychological) and the benefits and sacrifices components of value are tested within a broader neurological network that includes e-service quality and satisfaction, word-of-mouth and intention to switch. The hypothesized relationships are tested; using Partial Least Squares, on data collected through a postal survey from167 Iran-based SME organizations. The results confirm the significant, but the differential impact of the three types of risk on the two value components. Specifically, performance risk and financial risk are found to be significant determinants of benefits, while psychological risk impacts on perceptions of sacrifices. This chapter also provides evidence of the differential impact of the benefits and sacrifices components of value on satisfaction, and the existence of both direct and indirect impacts of these components on word-of-mouth and intention to switch.