Nowadays, more useful polymers constitute vinylic structure because of the extensive attention is being paid to these materials by the manufacturers. For this purpose, formulations under appropriate conditions are employed for the synthesis of vinylic polymers. Because of the presence of asymmetric carbon in repeating units, one of the most important parameters in vinylic polymers is tacticity and stereoregularity. Therefore, variations in polymerization process conditions can basically affect the stereoregularity of the vinylic monomers in polymer chains, and consequently result in polymers with specific properties. Nuclear magnetic resonance spectroscopy (NMR) is the most useful and powerful method for quantitative determination of stereoregularity and tacticity in vinylic polymers. As the polymers mainly consist of carbon and hydrogen, the NMR studies may be performed on these atoms with highest accuracy.