We introduce the walk-on-boundary (WoB) method for solving boundary value problems to computer graphics. WoB is a grid-free Monte Carlo solver for certain classes of second order partial differential equations. A similar Monte Carlo solver, the walk-on-spheres (WoS) method, has been recently popularized in computer graphics due to its advantages over traditional spatial discretization-based alternatives. We show that WoB's intrinsic properties yield further advantages beyond those of WoS. Unlike WoS, WoB naturally supports various boundary conditions (Dirichlet, Neumann, Robin, and mixed) for both interior and exterior domains. WoB builds upon boundary integral formulations, and it is mathematically more similar to light transport simulation in rendering than the random walk formulation of WoS. This similarity between WoB and rendering allows us to implement WoB on top of Monte Carlo ray tracing, and to incorporate advanced rendering techniques (e.g., bidirectional estimators with multiple importance sampling, the virtual point lights method, and Markov chain Monte Carlo) into WoB. WoB does not suffer from the intrinsic bias of WoS near the boundary and can estimate solutions precisely on the boundary. Our numerical results highlight the advantages of WoB over WoS as an attractive alternative to solve boundary value problems based on Monte Carlo.