Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As30S70 chalcogenide glass by using spin-coating method. The silica/As–S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As–S photonic crystal. Both, the infilled silica/As–S opal film (Δn ∼ 0.84 near λ = 770 nm) and the inverse opal As–S photonic structure (Δn ∼ 1.26 near λ = 660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ∼ 0.434 near λ = 600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated “inorganic polymer” opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.Graphical abstractSilica/As–S opal film template was prepared by spin-coating silica colloidal crystal film with nano-colloidal solution of As–S chalcogenide glass. Inverse opal As–S photonic crystal was then obtained by rinsing silica opal template in diluted HF acid.Research highlights► Colloidal crystallization under silicon oil method provides large area colloidal crystal film of silica (d ∼ 280 nm) with highly ordered in fcc (1 1 1) lattice. ► Chalcogenide glass of As30S70 forms in propylamine (CH3CH2CH2NH2) nano-colloidal solutions with cluster size d ∼ 2–8 nm in the concentration range 1–103 mg/ml. ► Low-cost spin-coating method allows proper in-filling of nano-colloidal solution of chalcogenide glass into silica opal film template. ► Inverse opal chalcogenide photonic crystal can be obtained by rinsing silica opal film template in hydrofluoric acid solution.