Sol–gel processing is an important colloidal processing route for the synthesis of macroporous materials of tunable microstructure. More recently, methods that use particle stabilized foams or emulsions have been developed. However, such methods generally involve the use of an external surface active additives that bind the particles together during processing. In this work, we present a simple and scalable additive-free method for the fabrication of porous materials that are both macroporous and microporous in nature. In particular, we show that silica-alumina porous materials can be fabricated by processing oppositely charged nanoparticle gel emulsions which are a dispersion of oil droplets in a space spanning network of colloidal particles. The nanoparticle gel emulsions obtained are initially characterized by optical microscopy and oscillatory rheology. The water and oil in these emulsion gels are removed by drying and it is finally sintered at 1000 °C to obtain porous material. The pore size and their distribution in the three-dimensional porous material is characterized using scanning electron microscopy (SEM) and X-ray tomography. Microscopy observations revealed a homogeneous distribution of macro-pores of 20–40 μm in diameter along the width, breadth and thickness of the porous material with an average porosity of 40% measured from 2D X-ray computed tomography images. One of the important features of the porous materials thus fabricated is the presence of nanosized pores due to the inherent porosity of the nanoparticle gel as well as micron sized pores due to the oil droplets.