Opium is a drug that was legal back in Poe's day. It can cloud the memory, induce visions, and blur the line between dreams and reality. In "Ligeia," it does all that – to our narrator. As such, we're forced to share in his habit, to see the world through drug-clouded lenses. His addiction is a sign of his suffering – you'd like to imagine he wouldn't be using the opium if Ligeia hadn't died – and it affects the very fabric of the story he's sharing. When he tells us that his hallucinations (the shadow on the carpet and the red drops in the goblet) might be the consequence of his opium high, we have to question everything he has been saying all along.
In "Ligeia," addiction is more than just a character trait; rather, it's a key plot device, a storytelling essential.
The narrator's addiction to opium is a consequence of his grief, and so a sign of his ultimately feeble will.