Electro-optic (EO) polymers are an attractive alternative to inorganic nonlinear materials. EO polymers with a Pockel's coefficient, r33, greater than 320 pm/V have been recently demonstrated. In addition to their high EO activity, EO polymers have the additional benefit that their dielectric constants at optical and millimeter wave frequencies are closely matched which allow for bandwidths which are limited only by the resistive losses of traveling wave electrodes. The amorphous nature of the host polymer makes heterogeneous integration of the materials on any substrate possible. The devices which will have the most immediate impact based on these recent materials developments are EO waveguide modulators. Performance benchmarks of less than 6 dB insertion loss, sub-volt Vpi and greater than 100 GHz bandwidth have been achieved separately however, the challenge of achieving all of these benchmarks in a single device has not yet been met. The aim of this dissertation is to optimize passive materials to achieve efficient in device poling of EO polymers, optimize the chromophore loading of the active polymers and to optimize waveguide modulators for device performance within a particular system, analog RF photonic links. These optimizations were done by defining figures of merit for the materials and modulators. This research strategy has led to significant improvements in poling efficiency as well as modulators with record low insertion losses which maintain a low Vpi on the order of 1--2 Volts. Using this optimization strategy and state of the art EO polymers, devices which meet or surpass the benchmark performance values in all categories are expected in the near future.