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Evening weddings tend to have a more formal atmosphere. Afternoon or morning weddings can range from quite casual (though not usually) to formal but they are usually somewhere in between.
Pick a nice dress that you could wear to church on sunday or on a nice date. You don't need anything longer than tea length and that length can go just about anywhere. As lurkette said go for the darker colors in the evening (though avoid the little black dress) and if it's in the afternoon then go with something lighter.
Don't worry too much about how overdressed or underdressed you are. If you pick something somewhat inbetween then you should look fine.
open toed shoes are fine, heals would be great.
Oh I just thought - if he's wearing a tux - then it's NOT casual at all. Your dress doesn't have to be formal and as a guest and not part of the wedding party you would be expected NOT to be dressed formally. But a nice dress anywhere from slightly above the knee to tea length could work. The longer dresses are what I would go for.
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