Hi Ken,
I guess the short answer is: "It depends!".
ADO has been around a while and works well for me with VFP front-end and middle tier, SQL Server back-end applications. There are native data providers available for some non-MS products and you can always use ODBC if you have to. I have a high comfort level with ADO. XML document generation is an integral part of ADO.
XML is the hot technology setup of the season. I've spent a lot of time getting up to speed on it and XSLT and can really see some cross-platform and transformational advantages in using them. With the recent production release of the MS parser, I see no reason not to start using XML to move data between tiers in new applications, especially if you're going to use a brower based front-end.
Also, don't forget about MSMQ as a messaging technology between the UI and business tiers. It really shines where you have users who need to work offline or where network connections are unreliable. I have only used it to transport ADO but there is no reason you can't use it with any data format that you can package.
Not much in the way of specifics, but I hope it helped.
Bob Tracy
Never engage in a battle of wits if you're only half armed.