The name and value columns for a PropertyGrid are generated in code, so they cannot be configured in XAML. They are designed to use star-scaling by default to prevent the need of a horizontal scrollbar.
You can make them auto-fit content if you wish though. You could put code like below (assuming column 0 is Name and column 1 is Value) either in a PropertyGrid-derived class' constructor, or in a Window that contains the PropertyGrid:
propGrid.Columns[0].MinWidth = 16;
propGrid.Columns[0].MaxWidth = double.NaN;
propGrid.Columns[0].Width = GridLength.Auto;
propGrid.Columns[1].MinWidth = 16;
propGrid.Columns[1].MaxWidth = double.NaN;
propGrid.Columns[1].Width = GridLength.Auto;
That code resets everything so it will fully auto-scale and show the horizontal scrollbar as needed.