Decentralized optimization algorithms have received much attention due to the recent advances in network information processing. However, conventional decentralized algorithms based on projected gradient descent are incapable of handling high-dimensional constrained problems, as the projection step becomes computationally prohibitive. To address this problem, this paper adopts a projection-free optimization approach, a. k. a. the Frank-Wolfe (FW) or conditional gradient algorithm. We first develop a decentralized FW (DeFW) algorithm from the classical FW algorithm. The convergence of the proposed algorithm is studied by viewing the decentralized algorithm as an inexact FW algorithm. Using a diminishing step size rule and letting t be the iteration number, we show that the DeFW algorithm's convergence rate is O(1/t) for convex objectives; is O(1/t(2)) for strongly convex objectives with the optimal solution in the interior of the constraint set; and is O(1/root t) toward a stationary point for smooth but nonconvex objectives. We then show that a consensus-based DeFW algorithm meets the above guarantees with two communication rounds per iteration. We demonstrate the advantages of the proposed DeFW algorithm on low-complexity robust matrix completion and communication efficient sparse learning. Numerical results on synthetic and real data are presented to support our findings.