Try something like this:
Dim file_is_CFBF As Boolean
Using fs = File.OpenRead("path to my file...")
Dim bytes(8 - 1) As Byte
Dim expected_bytes As Byte() = {&HD0, &HCF, &H11, &HE0, &HA1, &HB1, &H1A, &HE1}
fs.Read(bytes, 0, 8)
file_is_CFBF = bytes.SequenceEqual(expected_bytes)
End Using
MsgBox(file_is_CFBF)