I'm still not 100% sure of your underlying data and business logic, but here's one approach that might help.
I'm working off the following sample data:

Based on what your description above, it sounds like you have something similar to:

Which gives results:

It seems that you don't actually want to Sum TOTAL_CTN, rather this should be the same for every MaterialNo with the Sum only applied in the Grand Total.
As such you can change the Sub Total aggregation to Max and, since you're using Report Builder 3.0, you can then take the Sum of the group level aggregation values. The report will look like this:

Where the Grand Total expression is:
=Sum(Max(Fields!TOTAL_CTN.Value, "MaterialNoMax"))
In this expression MaterialNoMax refers to the name of the Row Group (based on MaterialNo in my example).
This gives your desired results:

The key here is thinking about what aggregation gets applied at each level and how these roll up to the end total.
SumofTOTAL_CTNfor your totals, I would expect a Grand Total of 12 based on the above data. Based on how you describe your grouping, I would also expect a Sub Total for each of rows in your report, but for CCC there is only one Sub Total, despite four different sizes. Can you please clarify: 1. Where the Sub Total grouping is applied? 2. How this affects the Grand Total? - Ian PrestonMaxof the individual TotalCarton rows? The average? Or will each MaterialNo group have the same TotalCarton value for each row, i.e. there isn't actually any aggregation applied? For CCC you have four rows, each with TotalCarton = 1, so I would expect this toSumto 4? - Ian Preston