Background Despite clinical optimization of methadone doses, as many as 53% of patients experience significant and unacceptable levels inter-dose opioid withdrawal some of the time. Little is known about the relationship between perceived inter-dose opioid withdrawal and patient characteristics in methadone maintenance treatment. Methods Ninety stabilized MMT patients were recruited and divided into three satisfaction groups (holders (H), partial holders (PH), and nonholders (NH)) based on their perceived opioid withdrawal as assessed by a guided self-report process. A battery of subjective assessments was administered during the approximate trough methadone condition. The primary measures were the Subjective Opioid Withdrawal Scale (SubOWS), Hopkins Symptom Checklist-90 (SCL-90), Obsessive–Compulsive Drug Use Survey (OCDUS), Profile of Mood States (POMS), and Neo Personality Inventory (NEO). Results Nonholders experienced more opioid withdrawal (SubOWS—NH: 22.0 ± 8.8 vs. PH: 12.2 ± 8.2 vs. H: 9.3 ± 10.0, p < 0.001) and craving (OCDUS—NH: 11.4 ± 8.8 vs. PH: 6.4 ± 6.9 vs. H: 6.5 ± 6.2, p = 0.016). Holders experienced less Obsessive/Compulsive psychological distress (SCL-90—NH: 15.3 ± 8.1 vs. PH: 12.3 ± 7.3 vs. H: 6.6 ± 5.1, p < 0.001), Depression/Dejection (POMS—NH: 19.7 ± 13.7 vs. PH: 17.2 ± 13.2 vs. H: 7.9 ± 10.4, p = 0.002), and neurotic personality (NEO—NH: 63.3 ± 12.3 vs. PH: 60.9 ± 10.0 vs. H: 54.0 ± 8.8, p = 0.006). Partial holders had a less agreeable personality (NEO—NH: 44.2 ± 8.6 vs. PH: 38.0 ± 10.6 vs. H: 47.6 ± 11.7, p = 0.002). Conclusions Physical opioid withdrawal is an important factor in understanding patient satisfaction with MMT. However, patient characteristics, such as level of psychological distress and negative mood, may also need to be considered because of their relationship with perceived inter-dose opioid withdrawal symptoms and patient satisfaction.