Photochemical transformations are unique strategy in synthesis that enables us to access complex and structurally diverse organic scaffolds. However, the challenges in controlling the excited-state to perform stereoselective reactions left this method under-utilized. This dissertation describes a novel strategy that employs atropisomeric chromophores to perform stereospecific phototransformations. The success of this strategy is well established in thermal chemistry but not comprehensively investigated in photochemical transformations. This research largely relies on rotamer control in the ground state (NEER principle) wherein the axial chirality in the starting material was transferred to point chirality in the products upon excitation. The chapter 1 describes the principle differences between the asymmetric thermal and asymmetric photochemical reactions. Further, a survey of methodologies developed towards asymmetric phototransformations and their outcomes are described. A brief introduction about the atropisomeric systems in thermal chemistry and the preliminary investigations in phototransformations are also provided. In chapter 2, enantiospecific disrotatory 4π-ring closure of atropisomeric 2-pyridones were investigated. The differential axial chirality designed (sterics and H-bonding units) displayed distinct temperature and solvent dependency on the enantiospecificity of the reaction. Eyring plot was computed to calculate the differential activation enthalpy and entropy for the reaction. Also, the course of phototransformation was followed through single-crystal XRD to decipher the preferred mode of cyclization for a given isomer of 2-pyridones. The high-pressure racemization and photoreaction study revealed that pressure provided stable chiral axis even at elevated temperature resulting in higher enantiomeric excess (ee) in the photoproduct. The chapters 3-5 describe the [2+2]-photocycloaddition of atropisomeric enamide, maleimide and imine derivatives. The design features on these molecules allowed us to perform complementary reactions that are not observed in the literature. These modifications were significant improvement to “axial to point chiral” strategy that improves the versatility of the photoreactions. For example switching of the excited state in enamides, continuous flow visibleiv light photocatalysis of maleimides and unusual photocycloaddition of stabilized imines are notable features. This dissertation encompasses detailed studies on the mechanism, scope and photophysical studies on new atropisomeric chromophores such as 2-pyridones, enamides, maleimides and imine derivatives that provides excellent avenue to access chirally enriched building blocks.