SnO2 is a promising material for electro- and photocatalysis sensors. In the electrocatalysis field, SnO2 is able to serve as a stable catalyst support for PEMFC cathodes. In this work, SnO2 were synthesized using SnCl4 or SnC2O4 and polystyrene microspheres as a template. The materials were characterized by XRD spectroscopy, CHNS analysis, low temperature (77 K) N2 adsorption, mercury intrusion porosimetry (MIP) and SEM. The SnC2O4 decomposition resulted in obtaining SnO2 with high conductivity up to 0.275 S/cm according to impedance spectroscopy. The increase in aging time and PS loading improves SnO2 conductivity and stability. The potential cycling test in 1.0–1.5 V RHE range revealed that stability of the most stable SnO2 is higher than that of CB Ketjen Black EC-300J and comparable with that of Vulcan XC-72R. The ORR activities of Pt catalyst based on macroporous SnO2 showed values similar to those of Pt/SnO2 found in literature.