Other forms: surest; surer; sures
Being sure has to do with being certain, convinced, trustworthy, or dependable. You can trust a sure thing.
Besides being a synonym for yes, sure has to do with lots of kinds of dependability. If you have a sure eye, then you have good aim, maybe with shooting a basketball or throwing darts. If you're sure of yourself, you're confident. A sure thing or sure bet is something almost certain to happen. If you're 100% convinced of something, you're sure of it.