Porous silicon and its oxide can be converted into porous silicon oxynitrides by ammonia heat treatment. For example, ammonia treatment at 1000 °C for 1 h following 850 °C, 30‐min steam oxidation of porous silicon can result in up to 40 at. % nitrogen in the porous oxynitrides. These porous silicon oxynitrides are compositionally more uniform than ammonia‐nitrided thermal oxides which exhibit nitrogen buildup at the oxide layer interfaces. However, the order of the oxidation and nitridation treatment matters: nitrided oxidized porous silicon exhibits higher electrical breakdown strength than nitrided porous silicon or oxidized nitrided porous silicon.