The nanoscale modulation of material properties such as porosity and morphology is used in the natural world to mold the flow of light and to obtain structural colors. The ability to mimic these strategies while adding technological functionality has the potential to open up a broad array of applications. Porous photonic crystals are one such technological candidate, but have typically underachieved in terms of available materials, structural and optical quality, compatibility with different substrates (e.g., silicon, flexible organics), and scalability. We report here an alternative fabrication method based on the bottom-up self-assembly of elementary building blocks from the gas phase into high surface area photonic hierarchical nanostructures at room temperature. Periodic refractive index modulation is achieved by stacking layers with different nanoarchitectures. High-efficiency porous Bragg reflectors are successfully fabricated with sub-micrometer thick films on glass, silicon, and flexible substrates. High diffraction efficiency broadband mirrors (R≈1), opto-fluidic switches, and arrays of photonic crystal pixels with size<10 μm are demonstrated. Possible applications in filtering, sensing, electro-optical modulation, solar cells, and photocatalysis are envisioned.