Then is used to mark time or in a sequence of events; than is used to compare items.
I’m going to finish eating dessert first, and then I’ll wash the dishes.
The concert ended, then Sophie went to bed.
Is your sweater more expensive than mine?
It’s obvious—John is stronger than Joe.
The new restaurant is much better than the one we went to last week. So then, who wants to go?
Still unsure? Use then whenever you want to indicate what’s next, i.e. “then” comes something; use than whenever one thing is compared to another, i.e. “more than”, “less than”, etc.
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Loose and Lose