De Payens approached King Baldwin II of Jerusalem with eight knights, two of whom were brothers and all of whom were his relatives by either blood or marriage, in order to form the first of the Knights Templar.
The other knights were Godfrey de Saint-Omer, Payen de Montdidier, Archambaud de St. Agnan, Andre de Montbard, Geoffrey Bison, and two men recorded only by the names of Rossal and Gondamer. The ninth knight remains unknown, although some have speculated that it was Count Hugh of Champagne himself.
As Grand Master, he led the Order for almost twenty years until his death, helping to establish the Order's foundations as an important and influential international military and financial institution.
On his visit to England and Scotland in 1128, he raised men and money for the Order, and also founded their first House in London and another near Edinburgh at Balantrodoch , now known as Temple, Midlothian.
A biography of Hugues de Payen by Thierry Leroy identifies his wife and the mother of his children as Elizabeth de Chappes. The book draws its information on the marriage from local church cartularies dealing chiefly with the disposition of the Grand Master's properties, the earliest alluding to Elizabeth as his wife in 1113 and others spanning Payen's lifetime, the period following his death and lastly her own death in 1170.