EPSS provides electronic support to learners in achieving a performance objective; a feature which makes it universally and consistently available on demand any time, any place, regardless of situation, without unnecessary intermediaries involved in the process. The aim of this review is to develop a set of theoretical construct that provide descriptive power for explanation of EPSS and its roots and features within the software application examples (i.e., Microsoft SharePoint Server”v2.0” Beta 2, IBM Lotus Notes 6 & Domino 6, Oracle 9i Collaboration Suite, and Mac OS X v10.2). From the educational and training point of view, the paper visualizes a pentagon model for the interrelated domains of the theoretical framework of EPSS. These domains are: learning theories, information processing theories, developmental theories, instructional theories, and acceptance theories. This descriptive framework explains a set of descriptions as to which outcomes occur under given theoretical conditions for a given EPSS model within software examples. It summarizes some of the theoretical concepts supporting to the EPSS’ related features and explains how such concepts sharing same features with the example software programs in education and job training.