The invention relates to dispersions of holey graphene materials and applications thereof. According to the invention, a method of forming a graphene-based material includes: (1) treating a mixture including an etchant and graphene oxide sheets to yield formation of holey graphene oxide sheets; (2) dispersing the holey graphene oxide sheets in a re-dispersal solvent to yield a holey graphene oxidedispersion including the holey graphene oxide sheets; and (3) treating the holey graphene oxide dispersion under reducing conditions to yield self-assembly of the holey graphene oxide sheets into a graphene-based material.