Previous empirical studies have found a weak nexus between the use of information and communication technologies (ICT) for learning and students' outcomes. However, this literature has not considered the role that the countries' stock of human capital can have in the successful use of ICT for learning. In this paper, we test empirically the existence of complementarities between human capital and technology adoption for learning. We carry out an empirical analysis with PISA data from a large-scale sample of 363,412 students enrolled in 13,215 schools in 48 countries. We estimate a hierarchical linear model (HLM) of three levels: students, schools, and countries. Our results strongly support the evidence of a positive externality of the stock of human capital on ICT use for learning. When we consider the moderator-effect of the stock of human capital, we find that the negative outcome of ICT use on students' outcomes in mathematics, reading and science turns positive (greater and more positive the higher the stocks of human capital are). The greater the stock of human capital an economy has, the more benefits it can get from investments in ICT for learning.