The stability of water-in-CO2 (W/C) emulsions stabilized with poly(dimethylsiloxane)-b-poly(methacrylic acid) (PDMS-b-PMA) and PDMS-b-poly(acrylic acid) (PDMS-b-PAA) ionomer surfactants is reported as a function of surfactant architecture, pH, temperature, pressure, and droplet flocculation. For a given PDMS block length, the stability of the emulsion is correlated with the distance from the balanced state where the surfactant prefers the water and CO2 phases equally. When the pH starting at 3 is raised up to 5-6, the hydrophilic/CO2-philic balance of the surfactant increases, because of ionization of COOH, and the emulsion becomes more stable. At the pH of maximum stability, the emulsion becomes more stable with a decrease in the PDMS length, for a given ratio of block lengths, because of gelation of the flocculated 2-5 mu m primary droplets. W/C emulsions are stable with respect to sedimentation for >24 h and are resistant to coalescence for more than 7 days. Because of gelation, the W/C emulsions are more stable than water/hexane emulsions (at ambient pressure) formed at the same conditions. The addition of 20% hexane to CO2 as a cosolvent reduced flocculation in some cases to zero.