Shaped polymer particles present opportunities for enormous global impact in healthcare, consumer, and food industries, expanding to advanced functionalities such as programmable biodistribution profiles, encapsulation and release kinetics. Their deployment, however, has been limited owing to the inability of conventional polymerization processes like emulsion polymerization to create non-spherical shapes. Numerous new processes that have been engineered to fabricate shaped polymer particles in the past decade enable access to diverse shapes like ellipsoids, disks, dimpled particles, etc. However, they often rely on physical manipulation or seeded polymerization, and hence, are laborious and hard to scale owing to the elaborate multistep processing steps. In this dissertation, initiated chemical vapor deposition (iCVD) technique is employed to develop a new single-step process for synthesizing size-controlled shaped polymer particles. Nematic liquid crystals (LCs) are leveraged as model anisotropic solvent for performing polymerization to access non-spherical shapes and, as real-time display screen reporting the reaction dynamics. The real-time monitoring is engineered by the installation of a custom long-focal range microscopy setup over the iCVD reactor, capturing the LC optical output in situ during the entire iCVD-in-LC process in two modes – bright field mode capturing the polymerization dynamics and cross polarized mode capturing the LC intrinsic patterns indicative of its molecular order. A novel synthesis pathway during the free radical polymerization of divinylbenzene via iCVD-in-LC process has been charted. Precipitation polymerization growth pathway is followed twice, once in bulk LC, resulting in the formation of pDVB nanospheres, and a second time at the LC-solid interface resulting in synthesis of microspheroids. The nanospheres which are the primary morphology, continuously precipitate to the LC-solid interface, where they further assemble into microgel clusters whose shape and directionality is guided by the local LC molecular alignment. On further polymerization, microspheroids emerge from these microgel clusters. Additionally, tuning polymerization time and/or initiator concentration are identified as two effective strategies to manipulate the size distribution of microspheroids during the iCVD-in-LC process. Key energetic factors driving the synthesis pathway to microspheroids are elucidated, providing a fundamental new framework for engineering diverse new particle shapes.