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Aims To evaluate the impact of compliance on the therapeutic effects of Desmopressin, as well as the importance of establishing the voiding school for low-compliance children in primary monosymptomatic enuresis treatment. Methods Eighty-nine patients with primary monosymptomatic enuresis treated with Desmopressin were observed during the 2017–2020 at University Children’s Hospital Belgrade, Serbia. The average patients age was 7.7 ± 2.4 years; 65 (73%) were boys and 24 (27%) % were girls. After the 3 months of Desmopressin treatment, the effect of therapy was evaluated according to the compliance. After the treatment, low-compliance patients and their parents were suggested to visit a voiding school. Results A significant decrease in the median enuresis frequency was noticed during the Desmopressin treatment (25.0 (20.0–26.0) vs 10.0 (2.0–17.0) per month, before vs after treatment, respectively) (p < 0.001). Patients with low compliance had a poorer response to Desmopressin (p < 0.001). An median enuresis reduction in the good compliance group was 92.3% (86.7 -95%), while in the low compliance group was 28.6% (16.7–43.3%). After attending voiding school, there was a significant increase in compliance (p < 0.001), associated with an median percent decrease in enuresis of 84.0% (75.0–95.5%) (p < 0.001). Conclusion Compliance considerably influences the beneficial effects of Desmopressin. Patients with poor therapeutic effects should be evaluated for compliance and introduced to voiding school.