Human beings must develop many skills to cope with the large amount of challenges that currently exist in the world: media empowerment for an active and democratic citizenship, knowledge acquisition and conversion for lifelong and life-wide learning, 21st century skills for matching demand and supply in labor markets, and dispositional employability for unpredictable future career success. One of the tools for achieving these is online education, in which students have the chance to manage their own time, content, and goals. Thus, this paper analyzes these issues from the perspective of skills gained through e-learning and validates the Socio-Technical E-learning Employability System of Measurement (STELEM) framework. The research was carried out with former students of the Universitat Oberta de Catalunya. Exploratory and confirmatory factorial analyses validate several consistent and reliable scales in two areas: (i) employability, based on educational social capital, media empowerment, knowledge acquisition, knowledge conversion, literacy, digitalness, collaboration, resilience, proactivity, identity, openness, motivation, organizational culture, and employment security; and (ii) socio-technical systems existing in this open online university, based on its information and communications technology (ICT), learning tasks, as well as student-centered and organizational approaches. The research provides two new psychometrical scales that are useful for the evaluation, monitoring, and assessment of relationships and influences between socio-technical e-learning organizations and employability skills development and proposes a set of indicators related to human and social capital, valid in employability contexts.