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Abstract A surfactant-free oil-in-oil emulsion-templating method is presented for fabrication of monolithic polyimide aerogel foams using monomer systems that produce fast sol–gel transition. An aerogel foam is a high porosity (∼90%) material with coexisting meso- and macropores inherent to aerogels with externally introduced micrometer size open cells (macrovoids) that are reminiscent of foams. The macrovoids are introduced in polyimide sol using surfactant-free emulsion-templating of droplets of an immiscible liquid that are stabilized against coalescence by fast sol–gel transition. Three immiscible liquids – cyclohexane, n -heptane, and silicone oil – are considered in this work for surfactant-free emulsion-templating. The aerogel foam monoliths, recovered by supercritical drying, exhibit smaller size macrovoids when n -heptane and cyclohexane are used as emulsion-templating liquid, while the overall porosity and the bulk density show weak dependence on the emulsion-templating liquid.