E-government is a means of transformation of public administration and creation of qualitative and more efficient services to citizens. Previous research shows that a significant role in the successful implementation of e-government, among other factors, is played by the support from government officials. For successful implementation in the field of education, in a centralized educational system, such as the Greek one, it is important to investigate the factors that influence the education officials' intention to use e-government services. This research investigated, through questionnaire, the factors affecting the intention of 88 officials of the Ministry of Education, Research and Religious Affairs to use e-government services. The Theory of Planned Behavior was used as a theoretical framework. The results showed strong intention of use by the educational officials. The attitude towards behavior and perceived behavioral control explained 43.1% of the intention's variance. The findings offer a variety of theoretical and practical implications in order to use the Theory of Planned Behavior in the e-government field of the education administration.