I agree, if you can do this during your initial for loop then it would save doing more potentially redundant looping down the track.
I would also suggest including more detail in your code to at least show the definition of the variable that you're asking about.
It looks like your dictionary contains a list of strings for each key. I would strongly advise doing it in your datarow loop but here is some generic VB.net code that could have assisted if that option was not available:
' Specify the file path for the CSV file
Dim filePath As String = "errorOutput.csv"
' Generate CSV output
Using writer As New StreamWriter(filePath)
' Write the header (optional)
writer.WriteLine("Error Code,Description")
' Iterate through the dictionary
For Each kvp As KeyValuePair(Of String, List(Of String)) In errorDict
Dim key As String = kvp.Key
For Each value As String In kvp.Value
' Write the key and value to the CSV file
writer.WriteLine($"{key},{value}")
Next
Next
End Using