The synergistic integration of organo-, transition metal, and photocatalysis has garnered increasing attention for its potential to foster groundbreaking transformations characterized by heightened reactivity, efficiency, and stereo control. Since its discovery in the nineteenth century, carbonylation chemistry has risen as a versatile cornerstone in chemical industries, assuming a pivotal role in both bulk and fine chemical synthesis. Nonetheless, the extensive reliance on carbon monoxide as a carbonyl source raises profound safety apprehensions due to its pronounced toxicity, particularly evident in large-scale transportation and application. Recent focus has shifted towards the valorization of carbon dioxide as an abundant, benign, and renewable carbon reservoir. Yet, the industrial integration of carbon dioxide as a raw material remains constrained, primarily due to the thermodynamic and kinetic challenges involved. Addressing this issue requires potent catalysts capable of overcoming these barriers. Photocatalysis, orchestrated with precise catalysts and reaction media, has emerged as a potent strategy for carbon dioxide utilization, effectively engaging and activating large quantities of this compound. This lecture will present diverse examples of photo- and photo electrocatalytic activation of carbon dioxide employing various co-catalysts, with the overarching aim of transcending extant hurdles in carbon dioxide utilization and ultimately revolutionizing traditional carbon monoxide-based carbonylation chemistry with innovative solutions. Central objectives encompass fundamental explorations and refinement of the ionic liquid-co-catalyzed photocatalytic reduction of carbon dioxide to yield carbon monoxide under mild conditions. Additionally, the reactivity of resultant carbon monoxide with diverse organic substrates in supercritical carbon dioxide will be discussed, culminating in the inception of streamlined and continuous processes for the direct synthesis of high-value fine chemicals from carbon dioxide.