I'm going to assume your table structure is something like this
CREATE TABLE mytable (UserID integer, UserName varchar(20), [Date] datetime, [Time] varchar(8))
your time is stored as a varchar field because there is no time type in sql2005. This will display the min and max time per each user and date. There are two options, the first if your times are HH:MM:SS then you can just use the convert function. The second shows you an example of parsing it and building the date yourself.
SELECT
UserID,
UserName,
[Date],
CONVERT(varchar, MIN(CONVERT(datetime, [Time], 108)), 108),
CONVERT(varchar, MAX(CONVERT(datetime, [Time], 108)), 108)
FROM mytable
GROUP BY UserID, UserName, [Date]
ORDER BY UserID, [Date]
SELECT
UserID,
UserName,
[Date],
CONVERT(varchar, MIN(DATEADD(second, CAST(SUBSTRING(Time, 7, 2) AS integer), DATEADD(minute, CAST(SUBSTRING(Time, 4, 2) AS integer), DATEADD(hour, CAST(SUBSTRING(Time, 1, 2) AS integer), 0)))), 108),
CONVERT(varchar, MAX(DATEADD(second, CAST(SUBSTRING(Time, 7, 2) AS integer), DATEADD(minute, CAST(SUBSTRING(Time, 4, 2) AS integer), DATEADD(hour, CAST(SUBSTRING(Time, 1, 2) AS integer), 0)))), 108)
FROM mytable
GROUP BY UserID, UserName, [Date]
ORDER BY UserID, [Date]