Application of foam in various upstream operations, such as in enhanced oil recovery, has gained significant attention in recent years. A good foaming agent should generate a stable foam, must be thermally stable (>90 °C, typical reservoir temperature), must have a high tolerance to salinity, and should have low adsorption on the reservoir rock. In view of this, four thermally stable and salt-tolerant polyoxyethylene cationic gemini surfactants were synthesized with different spacers (mono phenyl and biphenyl) and different counterions (Br− and Cl−). Foaming properties were evaluated using initial foam generation, foam volume stability at a given time, bubble count, and average foam bubble radius. The effect of counterions and nature of spacers, with and without the presence of salts, on foaming properties was evaluated. It was found that number of phenyl rings (mono phenyl and biphenyl) had no significant effect on foamability and foam stability in the presence or absence of salts. However, the effect of counterions was prominent in deionized water. In deionized water, foam generated by gemini surfactants with bromide as a counterion was more stable compared to the foam generated using the surfactant containing chloride as the counterion. In saline solution, the type of counterion had no effect on the foamability or foam stability of the foam generated using synthesized cationic gemini surfactants. The foam volume stability decreased by the addition of salts; however, a further increase in salt concentration enhanced the foam volume stability. The synthesized surfactants showed good thermal stability, salt tolerance, and foaming properties and can be an attractive choice for upstream applications.