A method of making microstructures having re-entrant or doubly re-entrant topology includes forming a mold defining the negative surface features of the re-entrant or doubly re-entrant topology that is to be formed. In one embodiment, a soft or flowable material is formed on a first substrate and the mold is contacted with the same to form a solid, now positive surface having the re-entrant or doubly re-entrant topology. The mold is then released from the first substrate. The microstructures are secured to a second, different substrate, and the first substrate is removed. Any residual microstructure material located between adjacent microstructures may be removed to form the separate microstructures on the second substrate. The second substrate may be thin and flexible any manipulated into useful or desired shapes having the microstructures on one side thereof.