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Objectives: This study aimed to assess the progression from one substance dependence to another in a sample of treatment-seeking substance users. Materials and Methods: The present cross-sectional study was based on a consecutive sample of patients with substance use disorder attending a de-addiction service in North India. Information was gathered about the demographic details and substance use pattern from the patient, family members, and previous records using a structured questionnaire. Results: Two hundred seventy-three patients out of 406 consecutive participants were dependent on more than one substance of abuse (67.2% of the sample). Most of the subjects were male, married, employed, and of urban background. In this sample of 273 patients, the substance of first dependence in descending order of frequency was tobacco, opioids, alcohol, and cannabis. Of those patients who had become dependent on opioids, it was the initial substance of dependence among 51.3%. Conclusion: Initial dependence to illicit substances without progressing through “gateway” of alcohol and nicotine dependence can occur due to socio-cultural influences. Knowing the sequence of dependence to substances can help design focused preventive measures.