We studied crystal structures in a monolayer consisting of anisotropic branched colloidal (nano)octapods. Experimentally, octapods were observed to form a monolayer on a substrate with a square-lattice crystal structure by dropcasting and fast evaporation of solvent. The experimental results were analyzed by Monte Carlo simulations using a hard octapod model consisting of four interpenetrating spherocylinders. We confirmed by means of free-energy calculations that crystal structures with a (binary-lattice) square morphology are indeed thermodynamically stable at high densities. The effect of the pod length-to-diameter ratio on the crystal structures was also considered and we used this to constructed the phase diagram for these hard octapods. In addition to the (binary-lattice) square crystal phase, a rhombic crystal and a hexagonal plastic-crystal (rotator) phase were obtained. Our phase diagram may prove instrumental in guiding future experimental studies. KEYWORDS: Octapods, nanocrystals, quasi-2D, self-assembly, anisotropy, colloids T he study of nanocrystal monolayers offers many opportunities for the creation of new materials with bulk properties that differ substantially from the materials that form by self-assembly in three dimensions. 1,2 This has led to a strong experimental and simulation interest in the behavior of nanocrystals in a (quasi-)2D geometry, that is, three-dimensional (3D) particles confined to a two-dimensional (2D) geometry. For instance, the seemingly simple system consisting of monodisperse hard disks in a 2D plane has sparked intense debate on the nature of the 2D solid−liquid phase transition. 3−6 In addition, experiments and simulations 7−14 showed that rod-and square-shaped convex anisotropic particles display a rich mesophase behavior when confined to a (quasi-)2D geometry.Advances in the synthesis of colloids and nanocrystals have resulted in monodisperse samples consisting of complex particles with anisotropic hard and soft interactions 15−21 and present many possibilities for further development in this field. Moreover, new simulation techniques are available to study the experimentally observed phenomenology for these new particles and to tackle the complex numerical problems such investigations bring about. 22−31 Only recently has the investigation into the phase behavior of anisotropic particles in (quasi-)2D by simulation been extended to the realm of nonconvex particles. 29 However, studying the phase behavior of nonconvex particles under confinement remains challenging due to geometric restrictions and the complex interactions between the particles. 32 Our group recently reported an experimental and simulation study of the hierarchical self-assembly of anisotropic branched colloidal nanocrystals, so-called octapods, into 3D superstructures in the liquid bulk phase. 20 In this Letter, we extend our findings to the formation of monolayers consisting of octapods, which were obtained by a deposition−evaporation procedure. In the experiments, we obtained monolay...