Particle-stabilized high internal phase emulsions have been used to synthesize tough and very high porosity macroporus polymers with a closed-cell pore structure. In this study, we show that Pickering water-in-oil emulsion templates with up to an 85 vol % internal phase can be stabilized by only 1 wt % of Mania particles with their surfaces suitably modified by the adsorption of 3.5 +/- 0.5 wt % oleic acid. The pore structure and mechanical properties of the resulting macroporous polymers were tailored by altering the internal phase volume ratio of the emulsion template and the titania particle concentration used to stabilize the emulsion templates. The pore size and pore size distributions increase with increasing internal phase volume of the emulsion template as well as decreasing Mania particle concentration used to stabilize the emulsion template. The mechanical properties, namely, Young's modulus and the crush strength of the macroporous polymers, increased with decreasing porosity and increasing foam density. The toughest macroporous polymer had the lowest porosity but also the smallest pore size and narrowest pore size distribution.