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The principal alkaloid found in opium is morphine. Morphine is the primary component that is extracted from the opium poppy and is widely recognized for its potent analgesic properties. It has been used historically in medicine to relieve severe pain and has a significant role in the treatment of various medical conditions.

While codeine, fentanyl, and heroin are all related to morphine, they are either derivatives or synthetics. Codeine is a less potent alkaloid that can also be found in opium, but it constitutes a smaller percentage of the substance compared to morphine. Fentanyl is a synthetic opioid that is not derived from opium but is similar in its effects. Heroin, on the other hand, is a semi-synthetic derivative of morphine, created through the acetylation of morphine, and is more potent than morphine but is not present in opium itself.

The dominance of morphine in opium makes it the principal alkaloid and a key substance in both historical and contemporary medicinal practices.