Emissions of particulate matters (PMs) and volatile organic compounds (VOCs) from open burning of biomass often cause severe air pollution; a viable approach is to allow biomass to burn in a furnace to collectively control these emissions, but practical control technologies for this purpose are lacking. Here, we report a hollandite manganese oxide (HMO) catalyst that can efficiently control both typical PMs and VOCs emissions from biomass burning. The results reveal that typical alkali-rich PMs such as KCl particles are disintegrated and the K(+) ions are trapped in the HMO "single-walled" tunnels with a great trapping capacity. The K(+)-trapping HMO increases the electron density of the lattice oxygen and the redox ability, thus promoting the combustion of soot PMs and the oxidation of typical VOCs such as aldehydes and acetylates. This could pave a way to control emissions from biomass burning concomitant with its utilization for energy or heat generation.