We present an interesting processing route for obtaining alumina/mullite-based ceramics with controlled porosity and airflow resistance leading to promising microstructures for application as sound absorbers. The use of ceramic materials aims for potential applications where high temperatures or corrosive atmospheres are predominant, e.g., in combustion chambers of gas turbines. For the production of the porous ceramics we combined freeze gelation and sacrificial templating processes to produce near-net-shaped parts with low shrinkage (<3%) based on environmental-friendly and low cost conditions. The obtained microstructure presents a bimodal pore size distribution, with small pores derived from the freeze gelation process (~30 μm) connecting large pores (2–5 mm diameter) originated from the expanded polystyrene template particles. These connections, called “windows” in this study, show a significant impact on the sound absorption properties, allowing the pressure diffusion effect to take place, resulting in a significant improvement of the sound absorption coefficient. By varying the template particle content and the slurry solid content, it is possible to control the sound absorption behavior at different frequencies of the open-celled ceramics. These ceramics feature a high open porosity, from 77% to 82%, combined with sufficient compressive strength ranging from 0.27 to 0.68 MPa and sound absorption coefficients of 0.30–0.99, representing a highly promising combination of properties for noise control and reduction at corrosive environments and high temperatures.