Underwater adhesion has numerous potential medical, household, and industrial applications. It is typically achieved through covalent polymerization and cross-linking reactions and/or the use of highly specialized biological or biomimetic polymers. As a simpler alternative to these covalent and biomimetic strategies, this article shows that stiff, gel-like complexes that adhere to various substrates under water can also be prepared through the ionic cross-linking of common, commercial polyelectrolytes. The gels form spontaneously when synthetic polycations, such as poly(allylamine) (PAH), are mixed with strongly binding multivalent anions, pyrophosphate (PPi) and tripolyphosphate (TPP). The PAH/PPi and PAH/TPP gels exhibit very high storage moduli (G'(infinity) approximate to 400 kPa), self-heal when torn, and adhere to both hydrophilic and hydrophobic substrates under water (with short-term tensile adhesion strengths of 350-450 kPa). Furthermore, these gels can be dissolved on demand (if adhesion needs to be reversed) by changing the ambient pH, which controls the ionization state of the polyelectrolyte and ionic cross-linker. These properties suggest that synthetic polycations cross-linked with PPi and TPP ions could provide a simple, inexpensive, and scalable platform for underwater adhesion.