How much to pay dog sitter to pick up dog after the ceremony

I imagine any sort of service through a company like that will have standard rates, and will tell you what those rates are, not the other way around. It's not just mileage though, it's also their time.

It depends on the sitter with Rover. They can set their rates.
we have two dogs, we are being charged 35$/day for them to be watched. Then we are being charged 100$ for the sitters to bring them to us (2.5 hr drive) for pictures and then take him home (another 2.5 hrs home).

The pet sitter will tell you what their rate is. My pet sitter charges me $25 per visit. All this includes is her checking on the food and water and giving my dogs potty breaks. She doesn't charge me mileage because I'm close to where she is. Most pet sitters do charge mileage though if you are outside their normal territory.

We are paying someone $95 to watch our three dogs and to pick them up after the ceremony. We still are working out details though with her. We live 25 min from the venue and are paying here $20 to drive them. That's included in the $95.

I did something similar for a friend recently and they gave me $30 to drive an hour total. I thought that was fair. But for a wedding I would probably expect a bit more. $50 perhaps?

You're actually going to want more than pick up and drop off. Weddings have a lot of moving parts and having a grown-up there just to watch your baby and make sure he is exercised (so that he's not full of energy), clean and put of trouble. Talk to your vet about who they most trust.
I have worked with dogs for years (vet tech, dog walking, boarding) and I wouldn't do it less for $100 unless I had a previous relationship with you.

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Hi Rica! Thank you for the response! This is more of what we are looking for just want to make sure we compensate correctly and wanted to see if anyone else had done something similar. I was thinking $50 for someone to pick him up after the ceremony/pictures and drop him off at my parent's house who have a big back yard and dog run. We would leave food and water so they wouldn't need to do any of that either

20 +miles is far no way would I do that for $50. In the DC area there are a few business that do this in the $150-$300 price range based on needs. And to me a basic need is a mile or 5 down the road. Put some feeler out there and see how it goes!