We investigate effects of two spin-coating parameters, relative humidity (5% <= RH <= 80%) in ambient atmosphere and water content Q wt % <= f(H2O) <= 20 wt %) in solution (rich in tetrahydrofuran), on the structure of breath figures (BF)formed in spin-cast films of polar poly(methyl methacrylate) (PMMA) and PMMA mixed with nonpolar polystyrene (PS). Film morphologies, examined with atomic and lateral force microscopy, are analyzed with integral geometry analysis to yield morphological BF measures. In PMMA, water added to solution has much stronger impact than that from moisture on formed BFs, which Could be ordered (with conformational entropy S similar to 0.9-1.0). In PMMA/PS, BFs decorate exclusively polar PMMA domains, resulting in morphologies with two length scales (sub-micro meter BFs and domains > 10 mu m). This suggests a novel strategy for herarchic structure formation in multicomponent polymer films. In PS/PMMA, BFs are better developed than in pure PMMA spin-coated in identical conditions. These observations show that the air boundary layer facing the spin-cast polymer film (region) is more important than the ambient atmosphere.