The progression from prescription opioid (RXO) abuse to RXO addiction is not well understood in adolescents, nor is the progression from RXO addiction to heroin abuse. The purpose of this pilot study was to characterize the development of RXO drug abuse, RXO drug addiction, and heroin abuse in a small cohort of adolescents recovering from opioid addiction at Massachusetts Recovery High Schools (RHS). A self-report questionnaire was administered to 31 adolescent, former RXO abusers across two Massachusetts RHS. RXO abuse was primarily initiated due to curiosity; RXOs were initially obtained through illicit and licit methods. Fifty-eight percent (N = 18) of the RXO abusers became addicted to RXOs. Many addicted adolescents initiated RXO abuse under the influence of marijuana, yet believed that they became addicted due to the stress from difficult life situations. A subgroup indicated they abused and became addicted to RXOs that had been obtained from legitimate prescriptions due to their pain. Sixteen percent (N = 5) of the sample abused heroin. Most heroin abusers (4/5) were addicted to RXOs prior to onset of heroin use. Heroin abusers indicated that they considered using heroin after they began tampering with RXOs. A portion of the sample felt that abuse deterrent formulations (ADFs) would have reduced their RXO use. This pilot study discovered areas where further research could be targeted, such as drug combinations, adolescent coping mechanisms, adolescent pain management, and the use of ADFs to disrupt the transition from RXO addiction to heroin use.