Taiwan's Government web portal has been the sole communication link between citizens and E-Government since being launched in 2002 to provide citizens with government-related information promptly via effective classification. The assessment of the service quality and citizens' satisfaction with E-Government has rarely been explored. The present study explored how the service quality of E-Government subsequently affects the users' psychological and behavioral responses. A structural model was proposed that contained four constructs: service quality, service value, users' satisfaction, and behavioral intention as well as their interrelations. A survey was used to collect users' ratings. Structural equation modeling was applied to verify the factor analysis of the obtained data and fit of a model. Analyses indicated adequate fit of model as follows: E-Government service quality --> service value --> users' satisfaction --> behavioral intention.