Phosphodiesterase type 5 inhibitors (PDE5i) are among the first line treatment options in men with erectile dysfunction (ED). On-demand sildenafil has proved to be an effective PDE5i but with lower spontaneity scores compared to daily tadalafil treatment. We aimed to investigate the impact of on-demand sildenafil compared to bedtime use on efficacy and spontaneity scores in men with ED. We retrospectively analysed data from a cohort of men with mild/moderate ED treated for three months with on-demand sildenafil 50 mg oral suspension formulation (OSF) (group 1, n = 40), bedtime sildenafil 50 mg OSF (group 2, n = 40) and bedtime sildenafil 37.5 mg OSF (group 3, n = 40). After three months patients were evaluated with the International Index of Erectile Function-5 items (IIEF-5) and the Psychological and Interpersonal Relationship Scales-Short Form (PAIRS-SF) questionnaires. Propensity score matching was used to adjust for baseline confounders. The IIEF-5 and PAIRS-SF scores were compared between groups at follow-up with the repeated measures ANOVA test. Linear regression analyses tested the associations between study variables and spontaneity scores. After matching, median patient's age and ED duration were 56 (50-61) years and 18 (10-20) months, respectively. Compared to baseline, IIEF-5 scores significantly improved after sildenafil OSF treatment, irrespective of the therapeutic approach (all p < 0.01 vs. baseline). The PAIRS-SF spontaneity score was significantly better in group 2 [15 (13-16), p < 0.01] and group 3 [14 (14-16), p < 0.01] compared to the on-demand use [13 (12-13)]. Fewer time concerns were reported for bedtime use than on-demand sildenafil. Sildenafil OSF bedtime use was found to be an independent predictor for better spontaneity and fewer time concerns scores (all p < 0.001). Bedtime sildenafil OSF showed similar efficacy but better spontaneity scores than on-demand use. Bedtime sildenafil is a valuable option for men with ED prioritizing efficacy and sexual spontaneity.