There’s an 1862 10 cent note with his picture on it, any earlier?
Since the United States government didn’t issue paper money prior to 1862, the answer would be NO. But, since individual states and private banks issued banknotes for over fifty years before that, the answer would be YES, there were banknotes issued in the US before 1862 with George Washington’s portrait on them. I quickly found some issued in Pennsylvania in the 1830’s.