The crosslinking reaction of pure poly(acrylic acid) and its blend with poly(vinyl alcohol) was studied by FT‐IR spectroscopy. It is demonstrated that also in blends the anhydride formation characteristic for pure poly(acrylic acid) is the predominant crosslinking reaction upon heating. But the ester formation between poly(vinyl alcohol) and poly(acrylic acid) is detectable due to the ester C=O vibrations and C—O—C vibrations, respectively. The degree of swelling and the Young's modulus of the crosslinked blend in deionized water depend on the time and temperature of the heat treatment. In dependence of the pH‐value of the swelling agent the blends swell or shrink. The working energy at the shrinking or swelling process induced by a change of the pH‐value of differently treated blends was measured. The values are in a range of technical interests and comparable with other microactuators.