The answer would require complete lists which are not available.
For the Saxons an early EK II got Oberleutnant Clemens on 24 September 1914.
Rudolf Berthold is a good candidate for early awards but he was still an
observer. He got the first EK II of the German 2. Armee on 13 September 1914 in his hand. EK I was handed over to him on 4 October 1914.
Von Hiddessen has had a very early EK I.
The "Tannenbergflieger" are worth a research too. As well some Bavarians.