In multicultural education and especially in the education of special groups (Roma, immigrants, etc.), the compatibility between educator and learners directly affects the efficiency and the outcome of the educational programs. This chapter presents a framework for the e-education of educators of special groups based on and aiming to improve their compatibility with their learners, code named “the ESG Framework,” as well as a case study on educators of Roma in Greece, through which the efficiency of the ESG Framework was confirmed. The ESG Framework, standing in the crossroads of learning technology, multicultural education, and adults’ education, combines the necessary elements from all these main fields. In each phase of its structure, the ESG Framework provides clear guidelines to be followed by designers, developers, administrators, and instructors for the effective and measurable improvement of compatibility between educators of special groups and their learners.