A few of my favorite couples:
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This was a James and Lily Potter that I did in one of my old neighborhoods. They were naturally attracted to each other, so I didn't have to do much.
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Here's Arthur and Molly, another couple who always went searching for each other when free will was turned on.
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This was my favorite couple, by far--a sim version of me, and my real-life ex, Tommy, made into a sim. I didn't think we'd make it, but we did, and we won a HUGE bonus, enabling us to build a mansion. We had a daughter (who was adorable...before the neighborhood got deleted by mistake) and a son (who I never really got to play before the neighborhood went bye-bye.
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and this was a video snapshot I made of us (not sure if it will show):