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The most widely used methods for toolpath planning in fused deposition 3D printing slice the input model into successive 2D layers in order to construct the toolpath. Unfortunately slicing-based methods can incur a substantial amount of wasted motion (i.e., the extruder is moving while not printing), particularly when features of the model are spatially separated. In recent years we have introduced a new paradigm that characterizes the space of feasible toolpaths using a dependency graph on the input model, along with several algorithms to search this space for toolpaths that optimize objective functions such as wasted motion or print time. A natural question that arises is, under what circumstances can we efficiently compute an optimal toolpath? In this paper, we give an algorithm for computing fused deposition modeling (FDM) toolpaths that utilizes Monte Carlo Tree Search (MCTS), a powerful general-purpose method for navigating large search spaces that is guaranteed to converge to the optimal solution. Under reasonable assumptions on printer geometry that allow us to compress the dependency graph, our MCTS-based algorithm converges to find the optimal toolpath. We validate our algorithm on a dataset of 75 models and show it performs on par with our previous best local search-based algorithm in terms of toolpath quality. In prior work we speculated that the performance of local search was near optimal, and we examine in detail the properties of the models and MCTS executions that lead to better or worse results than local search.