Also please use some spaces in your equations, you use plenty of white space everywhere else

Also please use some spaces in your equations, you use plenty of white space everywhere else.

I have a minute or two so I will also say this...

since this is going over so many records and that simple Variable freed up a good 10 seconds, I think that it might be worth it to move as much static calculation out of the query as possible, I know this is less about what SQL was meant for, but I also think this is more about being Dynamic as well.

Maybe I am going a little too far here, but this should still do the same thing as the original

create function [dbo].[BucketString] (
    @values varchar(max),
    @bucketSize int,
    @bufferSize int = 1,
    @offset int = 0)

returns @result table (id int, item varchar(max))

begin

    DECLARE @bucketAndBufferSize
    DECLARE @maxID
    DECLARE @bufferMinusBufferMinusOne
    DECLARE @bufferMinusOne
    
    SET @bucketAndBufferSize = @bucketSize+@bufferSize
    SET @maxID = LEN(@values) / (@bucketAndBufferSize) + 1
    SET @bufferMinusBufferMinusOne = @bufferSize - (@bufferSize - 1) 
    SET @bufferMinusOne = @bufferSize - 1
    
    with buckets as
    (   
        select 1 id

        union all

        select t.id + 1
        from buckets t
        where id = t.id 
            and t.id < @maxID
    )

    insert into @result
    select 
        id, 
        substring(@values, @offset + ((id - 1) * @bucketAndBufferSize + (case when @bufferMinusOne = 0 then 1 else @bufferMinusBufferMinusOne end)), @bucketSize) string
    from buckets    
    option (maxrecursion 0)

    return;

end

I apologize for the mismatched casing, it's habit to capitalized those words...

When bufferSize is unchanged you want it to be 1 so let's just do that and take out the extra call to the variable.

I took out all the arithmetic that wasn't reliant on information from the query and made them their own variable, this isn't going to be a huge difference, but I think it will be faster than doing the arithmetic inside the query itself, it's like being distracted by that red ball all the time, it distracts you momentarily but you get the job done.