This dissertation pertains to the investigation of innovative technologies to generate high performance anisotropic microcellular materials with unusual morphologies to understand the mechanisms of anisotropic formation and systems to control the structure and ultimate properties. First, a convenient and energy efficient method to produce anisotropic high performance polymeric foams via radically initiated cationic frontal polymerization (RICFP) coupled with chemical blowing agents (CBA) is presented. The results illustrate the development of anisotropy within frontal polymerization (FP) foam formation results from the propagating front working in concert with foam volume expansion. This can be controlled through changes in boundary conditions and front initiation position, which affect the microcellular structure and the physical and mechanical properties. Formulation changes, through the addition of nanoparticles, also affect the properties, microcellular characteristics, and kinetics of the FP process. Additionally, a similar method was developed where the microcellular structure and anisotropy is dictated by the directionality of the propagating front during RICFP from a free-standing gel and not by external confinement. This is DocuSign Envelope ID: 0570F892-1B1E-4799-9F90-7FDB4E1F15C3 viii achieved by first creating a gel where the crosslink density can be tuned by UV intensity and cure time, after which can be foamed while simultaneously creating a second network via RICFP. In this case, the microcellular morphology and ultimate properties are dictated and can be tuned through manipulating the crosslink density of the gel precursor or the formulation. Moreover, by patterning the crosslink density of the initial gel through controlled UV exposure, complex microcellular structures can be formed that are not possible in conventional foaming processes. Solid-state foaming was performed via supercritical-CO2 and superheated-water as green solvents, on an anisotropic media (e.g., fiber) to investigate how molecular orientation affects the resulting anisotropic microcellular structure. Further investigation into the use of this strategy to generate complex microcellular hierarchical constructs by templating assemblies of helically biased fibers was performed to understand their effect on the corresponding deformation. It was found that the anisotropic microcellular structure follows the direction of molecular orientation, resulting in a complex deformational response imposed by the template. That is, foams generated to create a helical bias are shown to undergo torsional deformation commensurate with uniaxial deformation when compressed uniaxially.