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FROM http://www.nationaldayofprayer.org/prayer05.php:

As our nation looked for a president to guide this new land, they unanimously chose GEORGE WASHINGTON. As President, he spent time on his knees in prayer twice a day. At 4:00 each morning and again at 9:00 each evening, he would go to his library, fall to his knees before a chair as he prayed before an open Bible.

In his First Inaugural Address, Washington "went further than he had ever gone before in stressing the role of God in the birth of our nation. Speaking with deep gravity, these were his words:

It would be peculiarly improper to omit, in this first official act, my fervent supplications to that Almighty Being, who rules over the universe, who presides in the councils of nations, and whose providential aids can supply every human defect, that His benediction may consecrate to the liberties and happiness of the people of the United States…No people can be bound to acknowledge and adore the invisible hand which conducts the affairs of men more than the people of the United States…"

It was Washington who in 1789 issued the first presidential proclamation for prayer as he proclaimed a National Day of Thanksgiving stating:

"It is the duty of all nations to acknowledge the Providence of Almighty God, to obey His will, to be grateful for His benefits, and to humbly implore His protection and favor...

The civil Government, though bereft of everything like an associated hierarchy, possesses the requisite stability, and performs its functions with complete success, whilst the number, the industry, and the morality of the priesthood, and the devotion of the people, have been manifestly increased by the total separation of the church from the State (Letter to Robert Walsh, Mar. 2, 1819).

Strongly guarded as is the separation between religion and & Gov't in the Constitution of the United States the danger of encroachment by Ecclesiastical Bodies, may be illustrated by precedents already furnished in their short history (Detached Memoranda, circa 1820).

Every new and successful example, therefore, of a perfect separation between the ecclesiastical and civil matters, is of importance; and I have no doubt that every new example will succeed, as every past one has done, in showing that religion and Government will both exist in greater purity the less they are mixed together (Letter to Edward Livingston, July 10, 1822).
I must admit moreover that it may not be easy, in every possible case, to trace the line of separation between the rights of religion and the civil authority with such distinctness as to avoid collisions and doubts on unessential points. The tendency to a usurpation on one side or the other or to a corrupting coalition or alliance between them will be best guarded against by entire abstinence of the government from interference in any way whatever, beyond the necessity of preserving public order and protecting each sect against trespasses on its legal rights by others. (Letter Rev. Jasper Adams, Spring 1832).