You can move and resize user slices in Photoshop, but not in the Save For Web & Devices dialog box.
To move a slice, move the pointer inside the slice selection border, and drag the slice to a new position. Press Shift to restrict movement to a vertical, horizontal, or 45° diagonal line.
To resize a slice, grab a side or a corner handle of the slice, and drag. If you select and resize adjacent slices, common edges shared by the slices are resized together.