Dense SnO2 based ceramics are widely used. In this paper, 95SnO2-5MnO2 ceramics were prepared by pressureless sintering in air at different temperatures. Phase compositions and microstructures are examined by XRD, SEM and EDX, respectively. The SEM results show that different morphologies exist at the SnO2 grain boundary of ceramic, which compose of manganese oxidation, testified by EDX. The different manganese oxides phases, found by XRD, are the source of oxygen concentration at the grain boundary during heating and oxygen dissipation when cooling. However, solid solutions of Mn, Sn and O are not observed. The density of 95SnO2-5MnO2 ceramics decreases with increasing the sintering temperature, due to the evaporation of SnO and decreasing concentration of oxygen at grain boundary in the cooling process. Densification of the ceramic is promoted with inhibiting the decomposition of SnO2 by increasing oxygen concentration in the heating process, but it is limited by the dissipation of oxygen at the grain boundary in the cooling process.