This study aimed to examine the impact of personality on glycemic regulation in adult patients with type 1 diabetes mellitus (T1DM). The study group consisted of subjects with T1DM, who were ≥ 18 years of age. The study was conducted in two phases: At baseline, subjects completed the Croatian version of the International Personality Item Pool scale (IPIP50s) and a questionnaire designed to gather socioeconomic data, duration of diabetes, presence of chronic complications, presence of cardiovascular risk factors, frequency, and type of pre-existing hypoglycemic episodes per week. Blood and urine samples were collected and body mass index (BMI) was calculated. Each participant was provided with the intermittently scanned glucose monitoring system (isCGM) Freestyle Libre. During the second visit (3 months from the start of the trial), glycemic parameters were collected from the reports generated from the Freestyle Libre system. Estimated glycated hemoglobin (HbA1c) values were significantly lower after three months compared to baseline HbA1c (Wilcoxon test, p < 0.001). An inverse correlation between the number of daily scans and degree of extraversion among subjects was observed, e.g., higher degrees of extraversion resulted in lower numbers of daily scans, while lower degrees of extraversion, i.e., introvertedness, resulted in higher numbers of daily scans (Rho = −0.238 p = 0.009). There was a positive correlation between emotional stability and time spent in hypoglycemia (Rho = 0.214; p = 0.02). In addition, a shorter duration of diabetes was associated with higher percentages of TIR and vice versa (p = 0.02). Investigating personality traits can be a useful tool for identifying patients predisposed to hypoglycemia and lower scanning frequency. Patients with a longer history of T1DM require closer follow-up and should be re-educated when necessary.