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So, why would someone be "smart" for paying more for the same product? This, to me, is stupid.
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A number of reasons. Maybe one airline's schedule works with yours better. Maybe you've got a business meeting that might go long, and if you have to miss your flight, you'd like the flexibility of having more flights to choose from. Maybe you've got elite status on one airline and you like getting on and off the plane first, and getting your bags first or the premium seating. Maybe one airline is just more convenient.
I don't mind spending $50 or $100 more to fly when I want to where I want. UAL tends to get my business because of their minihub at IAD. I can pretty much go anywhere I want non-stop, and it's usually a lot more convenient for me.
It doesn't matter if it's for business or pleasure, I spend the extra money because of the convenience factor. If it's business, it ain't my money. If it's for vacation, well, I'd rather spend time at my vacation site than changing planes!
I'm paying for the convenience there, kind of like how I pay more for 7-11 when I'm jonesing for a hot dog at 3 AM.