Herein we report the carbonylation of β-propiolactone and acrylic acid using [Co2(CO)8] as catalyst. For PL, we achieved quantitative yields and excellent selectivity in acetonitrile, under 15 bar of CO, 90 °C and 6 h reaction time. Scaling-up the reaction to 1 g batches does not undermine reactivity. Less toxic, recommended solvents are suitable for this reaction. Our catalytic system proves efficient for acrylic acid as well when H2 is added to the gas phase, in which case quantitative yields are obtained. Methylated variant of acrylic acid proved active under the depicted conditions, despite carbonylation proceeding with poorer performances. Better understanding of the reaction mechanism, of the catalyst deactivation pathways, and in-situ analysis of speciation species formed during [Co2(CO)8] solvent-induced disproportionation would be valuable to further improve this system and extend it to a wider variety of substrates.