Learning approaches describe the students’ degree of cognitive commitment to learning in diverse types of academic tasks and educational environments. Even though from a micro-level perspective different profiles of approaches have been identified in high-achievement undergraduates attending several majors, such profiles have not been examined from a macro-level approach in terms of distinct educational cultures. Therefore, the research involved two studies conducted on undergraduates from Argentina and Spain: The first one was aimed at analyzing the psychometric features of the Approaches and Study Skills Inventory for Students (ASSIST) whereas the second was focused on examining the learning approaches profiles of high and low achievers attending the same major (Psychology) in two different educational cultures (Spain and Argentina). The scale’s original internal structure, examined on a sample of 400 participants (50% Spanish), was verified except for one item, which was fatherly eliminated. The resulting structure was tested and proven verified in a new sample (N = 1,334; 58.3% Spanish) by confirmatory factor analysis, factorial invariance, and internal consistency studies. External validity evidence was examined as well. Additionally, norms to be used in the professional field were calculated. Profiles of learning approaches by academic achievement from each country were examined by latent class analysis. In both cases, high achievers reported higher and more frequent use of the Deep and Strategic approaches and lower and less frequent usage of the Surface one. Further studies should replicate these analyses in undergraduates attending other majors in order to test the hypothesis sustaining these findings’ generalization.