Polymeric materials have become ubiquitous in everyday life and have drastically impacted all aspects of societal living, from food and material packaging, biomedical advances, electronics, transportation, and much more. In order to keep up with the ever-growing demand for advanced polymeric materials, new synthetic methods must be developed as direct handles to tune polymer properties, processability, and application. Leveraging temporal control over polymer initiation is one way in which novel materials can be synthesized with augmented physical properties. The contents of this thesis describe two separate ways to achieve temporal control over polymer initiation. First, we have developed a new synthetic method to achieve temporal control over polymerization by metering in an initiator over time to target particular molecular weight distribution (MWD) shapes. Through this method, we have shown that we can directly influence polymer properties such as processability and material strength. Second, by taking advantage of visible light, we have established a new photocontrolled cationic polymerization method that provides for excellent temporal control of poly(vinyl ethers). Using small molar quantities of a photocatalyst, we can initiate and stop a polymerization at will by turning on or off the light, respectively providing a means for future applications in 3D printing and surface patterning. Lastly, this thesis will describe early efforts to develop an Iron-Atom Transfer Radical Polymerization (Fe-ATRP) using redox non-innocent ligands. Given that iron is one of the most abundant elements on earth, synthesis of polymers using iron catalysts can help reduce economical and environmental costs associated with metal catalyzed polymerization processes. Using a redox-non-innocent ligand around an iron catalyst thus provides a means for achieving stable catalysts to achieve a controlled Fe-ATRP.