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Increasing awareness of, and information about, overdose risk is an appropriate approach in risk reduction. e-Health technology in substance use disorders is an opportunity to support behavioral changes related to public health concerns. The present study aimed to evaluate the short-term impact of an innovative e-health psychoeducational software, the Overdose RIsk InfOrmatioN (ORION) tool. The ORION programme provided relevant information to opioid-dependent individuals about the risk of suffering a drug overdose as a result of high risky and dysfunctional behaviors. Seven aggregate risk factors were identified through a systematic review and their outputs included in a risk estimation model. We recruited 194 opioid-dependent treatment-seeking individuals from the United Kingdom, Germany, Italy, and Denmark. All participants were given at study entry, and after their use of the software, the General Self-Efficacy (GSE) Scale. We found comparable pre- and post-ORION administration mean GSE scores (SD), 28.49 (5.50) and 28.32 (5.90), respectively (p = 0.297). However, there was an inverse correlation between the number of risk factors and reported levels of self-efficacy (p < 0.001). ORION was able to identify individuals who are most in need of reducing their modifiable risk factors with appropriate interventions. However, a one-shot e-health tool cannot influence complex domains such as self-efficacy unless this is used with other effective interventions. Nonetheless, the ORION tool is unique in its style and content of delivery, that is translating risks combination into a clear estimation, and will need further development such as (a) integration in smartphone-based e-health apps and (b) testing in other high-risk populations.