In this work, we study two first-order primal-dual based algorithms, the Gradient Primal-Dual Algorithm (GPDA) and the Gradient Alternating Direction Method of Multipliers (GADMM), for solving a class of linearly constrained non-convex optimization problems. We show that with random initialization of the primal and dual variables, both algorithms are able to compute second-order stationary solutions (ss2) with probability one. This is the first result showing that primal-dual algorithm is capable of finding ss2 when only using first-order information; it also extends the existing results for first-order, but {primal-only} algorithms. An important implication of our result is that it also gives rise to the first global convergence result to the ss2, for two classes of unconstrained distributed non-convex learning problems over multi-agent networks.