Efficient mass transport and selective salt rejection are highly desirable for solar or thermally driven seawater desalination, but its realization is challenging. Here a new liquid supply mechanism is proposed, i.e., ionic pumping effect, using a polyelectrolyte hydrogel foam (PHF), demonstrated with poly(sodium acrylate) [P(SA)] embedded in a microporous carbon foam (CF). The PHF simultaneously possesses high osmotic pressure for liquid transport and a strong salt‐rejection effect. The PHF is able to sustain high flux of ≈24 L per m2 per hour (LMH), comparable to the evaporative flux under 15 suns, and a salt rejection ratio over 80%. Compared to the porous carbon foam without the polyelectrolyte hydrogel, i.e., with only the capillary pumping effect, the PHF yields a 42.4% higher evaporative flux, at ≈1.6 LMH with DI water and ≈1.3 LMH with simulated seawater under one‐sun condition due to the more efficient ionic liquid pumping. More importantly, thanks to the strong salt‐rejection effect, the PHF shows a continuous and stable solar‐driven desalination flux of ≈1.3 LMH under one‐sun over 72 h, which has not been achieved before. The successful demonstration of both efficient ionic pumping and strong salt rejection effects makes the PHF an attractive platform for sustainable solar‐driven desalination.