This should work just fine.
UPDATE table
SET UniqueIdentifierColumn = NEWID()
WHERE ...
Notice that doing the update in a single set-based statement populates each row with a different GUID.
Sample Code
CREATE TABLE dbo.HugeTable (
ColID int IDENTITY PRIMARY KEY,
ColGUID uniqueidentifier,
ColInt int
)
DECLARE @ct int
SET @ct = 0
WHILE @ct < 10 BEGIN
SET @ct = @ct + 1
INSERT INTO dbo.HugeTable (ColInt) VALUES (@ct)
END
GO
SELECT COUNT(*) AS Ct FROM dbo.HugeTable
UPDATE dbo.HugeTable
SET ColGUID = NEWID()
WHERE ColID BETWEEN 3 AND 7
SELECT * FROM dbo.HugeTable
Results
Ct
-----------
10
ColID ColGUID ColInt
----------- ------------------------------------ -----------
1 NULL 1
2 NULL 2
3 E45E13D8-CFF0-4FC7-B7C9-1D53E95C502D 3
4 33C3CCBC-B6BB-4CAA-AB10-338AA95F366E 4
5 82136767-396E-4B33-B9DD-FFD30FCF4680 5
6 EFA24EC9-F8F9-47CF-839F-D588F69D167F 6
7 546F7C14-BDDA-4226-B45C-B0DDCD43E7DB 7
8 NULL 8
9 NULL 9
10 NULL 10