Background: Given the limited evidence in the field, the present study aimed to explore the association of UPF intake with food literacy levels in an adult Mediterranean-based population. Methods: Self-reported demographic and anthropometric data were collected from 317 apparently healthy adults (52.5% males) Food literacy and dietary intake of this population were also assessed. Foods were classified as ultra-processed according to the NOVA system, and their contribution to total daily energy intake (%) was calculated. Then, participants were grouped into the (1) higher UPF intake (HUPFI), and (2) lower UPF intake (LUPFI) groups, based on the median value of this population as a cut-off. Results: Between-group analysis revealed that LUPFI scored statistically significantly higher than the HUPFI group in total food literacy (93.5 [84.0–104.0] vs. 86.0 [78.0–99.0], p < 0.001) and in three out of five food literacy sub-dimensions. Sub-analysis revealed no differences between LUPFI and HUPFI groups of individuals with normal weight. In participants with overweight or obesity, the LUPFI group scored lower than the HUPFI in the total food literacy score (95.0 [87.0–104.0] vs. 81.0 [70.0–94.0], p < 0.001) and in each sub-dimension. Conclusions: Higher UPF intake was associated, in adults with overweight or obesity, with lower levels of food literacy.