Nanoparticles are indispensable ingredients of solution-processed optical, dielectric, and catalytic thin films. Although solution-based methods are promising low-cost alternatives to vacuum methods, they can have significant limitations. Coating uniformity, thickness control, roughness control, mechanical durability, and incorporation of a diverse set of functional organic molecules into nanoparticle thin films are major challenges. We have used the electrostatic layer-by-layer assembly technique to make uniform, conformal multistack nanoparticle thin films for optical applications with precise thickness control over each stack. Two particularly sought-after optical applications are broadband antireflection and structural color. The effects of interstack and surface roughness on optical properties of these constructs (e.g., haze and spectral response) have been studied quantitatively using a combination of Fourier-transform methods and atomic force microscopy measurements. Deconvoluting root-mean-square roughness into its large-, intermediate-, and small-scale components enables enhanced optical simulations. A 4-stack broadband antireflection coating (<0.5% average reflectance in the visible range, and 0.2% haze) composed of alternating high-index (n approximately 1.96) and low-index (n approximately 1.28) stacks has been made on glass substrate. Films calcinated at 550 degrees C endure a one-hour-long cloth cleaning test under 100 kPa normal stress.