Prevention and control of hypertension and cerebro-cardiovascular diseases are associated with adequate sodium and potassium intake and adherence to a Mediterranean dietary pattern. The aim of this study was to assess the association between adherence to a Mediterranean diet (MD) and the excretion of sodium and potassium as surrogate measures of intake. This is a cross-sectional analysis as part of a larger study (the iMC SALT randomized controlled trial) among workers of a public university. A food frequency questionnaire was used to assess the adherence to MD, using the alternative Mediterranean diet (aMED) score; sodium and potassium excretions were estimated by 24-h urine collections. Sociodemographic and other lifestyle characteristics were also obtained. The associations between the adherence to MD and Na and K excretion were calculated by logistic regression, adjusting for confounding variables. From the 109 selected participants, seven were excluded considering urine screening and completeness criteria, leaving a final sample of 102 subjects (48% male, average age 47 years). Mean sodium and potassium excretion were 3216 mg/day and 2646 mg/day, respectively. Sodium and potassium excretion were significantly higher in men, but no differences were found according to different levels of MD adherence. In logistic regression analysis, sodium, potassium, and sodium-to-potassium ratio urinary excretion tertiles were not associated with MD adherence (low/moderate versus high), even after adjustment for confounding variables. A high adherence to MD was thus not associated with a different level of sodium and potassium intake.