The clinical learning environment, which includes the culture of clinical units, the mentoring process, and the different health organizations, influences the learning process of nursing students. However, scarce literature has been published on the impact of the clinical learning environment on first-year nursing students in long-term care. We aimed to assess first-year nursing students ‘preferred’ and ‘actual’ clinical learning environments when conducting their first placements in nursing homes within an innovative placement model that comprised the active participation of academic mentors. The validated Spanish version of the Clinical Learning Environment Inventory (CLEI) instrument was used in our study, and 99 first-year nursing students participated. The highest mean scores for the CLEI-Actual were found for the Satisfaction (22.7) and Involvement scales (19.09). The lowest mean scores were found for the Personalization (17) and Individualization (17.27) scales. The multiple correlation (R) between the Satisfaction and the other CLEI scales was 0.61 (p > 0.001), which means that in this study the association between student satisfaction and their perception of the clinical learning environment was strong. First-year students conducting their first clinical placements in nursing homes can have a positive learning experience considering a well-designed and organized pedagogical strategy, including constant support and feedback from academic and clinical mentors.