We introduce a novel and versatile approach for preparing self-assembled nanoporous multilayered films with tunable optical properties. Protonated polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and anionic polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films. BCM film growth is governed by electrostatic and hydrogen-bonding interactions between the opposite BCMs. Both film porosity and film thickness are dependent upon the charge density of the micelles, with the porosity of the film controlled by the solution pH and the molecular weight (M-w) of the constituents. PS7K-b-P4VP(28K)/PS2K-b-PAA(8K) films prepared at pH 4 (for PS7K-b-P4VP(28K)) and pH 6 (for PS2K-b-PAA(8K)) are highly nanoporous and antireflective. In contrast, PS7K-b-P4VP(28K)/PS2K-b-PAA(8K) films assembled at pH 4/4 show a relatively dense surface morphology due to the decreased charge density of PS2K-b-PAA(8K). Films formed from BCMs with increased PS block and decreased hydrophilic block (P4VP or PAA) size (e.g., PS36K-b-P4VP(12K)/PS16K-b-PAA(4K) at pH 4/4) were also nanoporous. This is attributed to a decrease in interdigitation between the adjacent corona shells of the low M-w BCMs, thus creating more void space between the micelles. Multilayer films with antireflective and photochromic properties were obtained by incorporating a water-insoluble photochromic dye ( spiropyran) into the hydrophobic PS core of the BCMs assembled in the films. The optical properties of these films can be modulated by UV irradiation to selectively and reversibly control the transmission of light. Light transmission of higher than 99% was observed with accompanying photochromism in the (PS7K-b-P4VP(28K)/PS2K-b-PAA(8K)) multilayer films assembled at pH 4/6. Our approach highlights the potential to incorporate a range of materials, ranging from conventional hydrophilic materials with specific interactions to hydrophobic compounds, into the assembled BCMs to yield multifunctional nanoporous films.