In one aspect, methods of patterning of thin films of an ionotropic polymer (e.g., poly(acrylic acid)) are provided. These processes can create micron or sub-micron-scale patterns of ionotropic polymers such as cation crosslinked poly(acrylic acid) (CCL-PAA). In one embodiment, patterning may be performed within microfluidic channels by flowing a solution of crosslinking agent (e.g., metal cations such as Ag+, Ca2+, Pd2+, Al3+, La3+, and Ti4+) that can crosslink a portion of an ionotropic polymer in contact with the solution. In another embodiment, methods of patterning ionotropic polymers involve photolithography. Upon patterning a positive photoresist (e.g., diazonaphthoquinone-novolac resin) on a film of CCL-PAA, the exposed regions of CCL-PAA can be etched by an aqueous solution. Advantageously, the patterned, crosslinked polymer may also serve as both a reactant and a matrix for subsequent chemistry. For example, in some embodiments, the initial crosslinking cation can be exchanged for a second cation that could not be patterned photolithographically. Patterned films of CCL-PAA can also be used to host and template the reduction of metallic cations to metallic nanoparticles, and to fabricate porous, low-k dielectric substrates.