SnO2/Zn2SnO4 HPMSs were synthesized by using self-made ZHS as sacrificial template. The shell thickness of the SnO2/Zn2SnO4 HPMSs is about 50 nm. The dominant pore size in the SnO2/Zn2SnO4 HPMSs is 5–20 nm. The formaldehyde sensitivity of the SnO2/Zn2SnO4 is improved by structural evolution.