We provide a novel framework to compute a discrete vector potential of a given discrete vector field on arbitrary polyhedral meshes. The framework exploits the concept of acyclic matching, a combinatorial tool at the core of discrete Morse theory. We introduce the new concept of complete acyclic matchings and we show that they give the same end result of Gaussian elimination. Basically, instead of doing costly row and column operations on a sparse matrix, we compute equivalent cheap combinatorial operations that preserve the underlying sparsity structure. Currently, the most efficient algorithms proposed in literature to find discrete vector potentials make use of tree-cotree techniques. We show that they compute a special type of complete acyclic matchings. Moreover, we show that the problem of computing them is equivalent to the problem of deciding whether a given mesh has a topological property called collapsibility. This fact gives a topological characterization of well-known termination problems of tree-cotree techniques. We propose a new recursive algorithm to compute discrete vector potentials. It works directly on basis elements of 1-and 2-chains by performing elementary Gaussian operations on them associated with acyclic matchings.