Carbon dioxide (CO2) gas is considered as an abundant and renewable C1 synthon for the preparation of highly valued chemicals. [1] Catalytic CO2 capture by propargylic substrates – alcohols or amines – affords α-alkylidene cyclic carbonates or carbamates, respectively. [2] Combination of CO2 capture with C–C cross-coupling reactions may give direct access to complex products that otherwise require multistep syntheses. [3] Such transformations are particularly desirable because they follow the principles of green chemistry for atom and step economy. We are accordingly presenting, herein, Pd-catalyzed carboxylative intermolecular or intramolecular C–C cross-coupling reactions on various propargylic alcohol substrates (see Fig. 1). Our experiments are supported by calculations based on density functional theory (DFT) method, which show that these reactions are exergonic because of product stabilization through the formation of additional C–C bonds, thus overcoming the thermodynamic and kinetic inertness of CO2 even under atmospheric pressure. Currently, our efforts are focused on the elucidation of the reaction mechanism.