The development of efficient and sustainable catalysts for multi-step transformations is central to advancing green chemistry. Herein, we report a non-noble metal tandem catalytic system for the hydroformylation–acetalization of alkenes, combining atom economy with operational simplicity. The catalyst was obtained by pyrolysis of crystalline ZIF-67, yielding cobalt nanoparticles embedded in a nitrogen-doped carbon matrix (Co@C600). This non-noble metal catalyst enables the one-pot transformation of alkenes to acetals using syngas and alcohols under relatively mild conditions (140 °C and 50 bar). The use of an environmentally benign solvent mixture of anisole with methanol proved essential for maximizing acetal yields and selectivity. Density functional theory (DFT) calculations revealed that nitrogen incorporation into the carbon support enhances aldehyde adsorption within the ideal energy range for catalytic turnover, explaining the superior activity observed. The system exhibited excellent recyclability and maintained high selectivity across terminal, internal, and cyclic alkenes. This work highlights the potential of earth-abundant metals and tandem catalytic strategies in developing greener synthesis of oxygenated fine chemicals.