Opioid consumption has increased worldwide, which carries the risk of opioid use disorder (OUD). However, the literature on OUD and opioid-related chemical coping (OrCC) in chronic noncancer pain (CNCP) is heterogeneous, with most studies conducted in the United States. We performed a multicenter, observational, cross-sectional study to address OrCC in long-term opioid therapy (LtOT) for CNCP in South Korea. The objectives were to determine the frequency and predictors of OrCC. We included 258 patients. Among them, fifty-five (21%) patients showed OrCC. The sample had high pain catastrophizing (≥30 points; 66%), moderate-severe insomnia (≥15 points; 63%), low resilience (68 points), and high suicidal ideation (67%). OrCC patients had greater pain interference (85.18% vs. 58.28%, p = 0.017) and lower satisfaction with the LtOT (56.4% vs. 78.3%, p = 0.002). In multivariable analysis, alcohol abuse (OR = 6.84, p = 0.001), prescription drugs abuse (OR = 19.32, p = 0.016), functional pain (OR = 12.96, p < 0.001), head and neck pain (OR = 2.48, p = 0.039), MEDD (morphine equivalent daily dose) ≥ 200 mg/day (OR = 3.48, p = 0.006), and ongoing litigation (OR = 2.33, p = 0.047) were significant predictors of OrCC. In conclusion, the break-out of OrCC in CNCP in South Korea was comparable to those in countries with high opioid consumption, such as the United States, regardless of the country’s opioid consumption rate.