In the past decade, astonishing improvements had been made in the performance and cost of consumer electronic devices. The main driving force behind this progress has been the reduction of the feature size on the integrated circuits, made possible by the advancements in microlithographic imaging technology. One of the essential components in the microlithographic imaging is the photoresist, a radiation-sensitive polymeric imaging material that allows the realization of circuit patterns on silicon wafers. This dissertation presents the synthesis, characterization, and evaluation of new positive and negative tone photoresist materials designed for use in 193 nm lithographic application. These materials are based on polymers with alicyclic structures in their backbone and have emerged as excellent platforms from which to design photoresists for 193 nm exposure. New photoresist materials based on poly(tetracyclo[188.8.131.52 2,5.17,12]dodec-3-ene-5-carboxylate-alt-maleic anhydride) have demonstrated etch resistance superior to that of conventional deep UV APEX-E? photoresists while providing as small as 80 nm resolution at 193 nm. This class of polymers has also been adapted to the design of high performance negative tone photoresists for 193 nm microlithography. New systems based on a polarity switch mechanism for modulation of the dissolution rate have been designed. These systems are based on new polar, alicyclic polymer backbones that include a monomer bearing a glycol pendant group that undergoes the acid catalyzed pinacol rearrangement upon exposure and bake to produce the corresponding less polar ketone. This photo-induced, acid catalyzed change in polarity can be translated into a change in solubility and thereby provides a basis for imaging. This monomer was copolymerized with maleic anhydride and a bis-trifluoromethylcarbinol substituted norbornene and the copolymer ratio was optimized to provide optimum imaging properties. New photoresist materials based on these terpolymers have demonstrated the excellent lithographic performance and have produced negative tone images as small as 90 nm in width.