Water becomes ordered in the form of hexagonal ice at room temperature under controlled humidity conditions upon confinement in the nanometer range between protective graphene sheets and crystalline (111) surfaces with hexagonal symmetry of the alkali earth fluoride BaF2. Interfacial water/substrate pseudoepitaxy turns out to be a critical parameter since ice is only formed when the lattice mismatch is small, an observation based on the absence of ice on (111) surfaces of isostructural CaF2 (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4798941]