Structured latexes provide a promising route to hard coatings without the use of coalescing aids. We studied the thermomechanical properties of films from structured soft-core/hard-shell hydrophobic latexes. We found that the mechanical properties of these films were closely related to their very particular organization. When the rigid phase was continuous, whatever its volume fraction, the films exhibited a high elastic modulus. An analysis of the viscoelastic properties of the films provided a good method for obtaining information about the interphase between the hard shell and soft core of the latex particles. By varying the film structure through annealing or the particle composition (core/shell ratio, core crosslinking, etc.), we were able to tune the mechanical properties of the films.