The Mediterranean Diet (MD) is characterized by a high intake of fruits and vegetables (FVs), which is considered as an important contributor to the beneficial effects of the MD pattern. In this cross-sectional study, we compared the food choices, evaluated by dietary habit questionnaires, of a sample of 995 adults, including 601 and 394 participants from Southern Italy and the Dominican Republic, respectively. In addition, we focused on their FV consumption, assessed by the Mediterranean Diet Adherence Screener (MEDAS) questionnaire, and on its association with skin carotenoid levels as measured by the Veggie Meter®. We found that a significantly higher percentage of Italians had five meals/day and breakfast compared to Dominicans (five meals/day: 43 vs. 25, p < 0.05; breakfast: 89 vs. 79, p < 0.05), whereas a lower percentage of participants from Italy consumed snacks between the two meals compared to the Dominican Republic population (47 vs. 70, p < 0.005). Most of the participants from both populations had breakfast at home. However, 59.3% of Italians and 27.5% of Dominicans (p = 0.005) had breakfast between 7:00 and 9:00 a.m., whereas 5.8% and 27.5% (p = 0.001) had breakfast after 9:00 a.m., respectively. Milk/yogurt and eggs were the most consumed foods for breakfast in Italy and the Dominican Republic, respectively. Regarding the main meals, most of the Italians and Dominicans had a first course for lunch and a second course for dinner. Of note, we observed that approximately half of the Italians ate FVs in their main meals and had a higher carotenoid score than the Dominicans. Interestingly, in the multiple linear regression analysis, we found that the carotenoid score was positively associated with sex (β = 0.078; p = 0.009), age (β = 0.008; p = 0.001), vegetable consumption (β = 0.12; p = 0.041) and the perception of a healthy diet (β = 0.12; p = 0.001) in the Dominic Republic population, while the carotenoid score was directly associated with sex (β = 54.97; p < 0.0001) and both vegetable (β = 25.42; p = 0.0008) and fruit (β = 38.61; p < 0.0001) consumption in the Italian sample. Our findings confirm the need to promote nutrition-based interventions to encourage FV intake, particularly in non-Mediterranean countries.