This paper investigates the application of the Six Sigma approach to improve quality in electronic services (e-services) as more countries are adopting e-services as a means of providing services to their people through the Web. This paper presents a case study about the use of Six Sigma model to measure customer satisfaction and quality levels achieved in e-services that were recently launched by public sector organisations in a developing country, such as Jordan. An empirical study consisting of 280 customers of Jordan's e-services is conducted and problems are identified through the DMAIC phases of Six Sigma. The service quality levels are measured and analysed using six main criteria: Website Design, Reliability, Responsiveness, Personalization, Information Quality, and System Quality. The study indicates a 74% customer satisfaction with a Six Sigma level of 2.12 has enabled the Greater Amman Municipality to identify the usability issues associated with their e-services offered by public sector organisations. The aim of the paper is not only to implement Six Sigma as a measurement-based strategy for improving e-customer service in a newly launched e-service programme, but also widen its scope in investigating other service dimensions and perform comparative studies in other developing countries.