Alumni volunteers are essential to Chi Psi's operations and offer valuable time and feedback to many areas of the Fraternity. The two leadership entities are the Chi Psi Executive Council, which oversees the governing affairs of the Fraternity, and The Educational Trust, which provides Brothers with leadership enhancement and personal development, as well as rewards scholarship and fosters positive relationships with the Fraternity.

The Chi Psi Executive Council was established in 1891 and has expanded to its current board of 16 members (11 alumni and 5 regional undergraduate representatives), the #7 (or National President), and all living past #7's. The Council is also assisted by an advisory board that currently seats 10 alumni. The Executive Council meets 3-4 times per year to implement the directives of the Annual Convention, oversee Central Office employees, grant preliminary Colony status to prospective Alphas, and ensure that Fraternity activity conforms with the Constitution and By-Laws. 

The Chi Psi Educational Trust was formed in 1926 as the first educational foundation in the fraternity world. The Trust works to develop, fund, and implement leadership and service programs, making them available to all undergraduates. This programming is known collectively as The Program for Excellence. In addition, the Trust provides scholarships and fellowships to undergraduate and graduate students of Chi Psi, respectively. The Trust gives out a number of awards in recognition of generous philanthropy and service to the community and to the Fraternity. There are currently 11 alumni Trustees.