Over recent decades Latin American countries have focused their education policies in the expansion of them. Some authors consider this achievement towards to the detriment of quality. But, what about the knowledge and skills of students? Equity in students achievement is defined consistently with the concept of equality of opportunity (Causa & Chapuis, 2010, pág. 4). Equal access to education is among the basic human rights and a component of well being. In this paper we aim to evaluate inequalities in learning opportunities for individuals coming from different socio-economic backgrounds, measured by PISA test scores (2009), as a proxy for inequality of opportunity. The analyses are made inside and cross-country differences in 6 countries of Latin America. Scores differences between students with high and low values of the Economic, Social, and Cultural Status index (ESCS) provide a measure of fairness of education in each country (OECD PISA reports 2001, 2004, 2007; Schutz et al., 2005, Schutz et al., 2007, Woessmann, 2004, d’Addio, 2007, cited by Causa & Chapuis, 2010). In this case, we applied a mean differences by student’s family and home background and we reinforce our results through Gini index, a conventional indicator.