The utilization of carbon dioxide as a polymer feedstock is an ongoing challenge. This report describes the catalytic conversion of carbon dioxide and an olefin comonomer, 1,3-butadiene, into a polymer structure that arises from divergent propagation mechanisms. Disubstituted unsaturated δ-valerolactone 1 (EVL) was homopolymerized by the bifunctional organocatalyst 1,5,7-triazabicyclo[4.4.0]­dec-5-ene (TBD) to produce a hydrolytically degradable polymer. Isolation and characterization of reaction intermediates using 1H, 13C, COSY, HSQC, and MS techniques revealed a vinylogous 1,4-conjugate addition dimer forms in addition to polymeric materials. Polymer number-average molecular weights up to 3760 g/mol and glass transition temperatures in the range of 25–52 °C were measured by GPC and DSC, respectively. The polymer microstructure was characterized by 1H, 13C, FTIR, MALDI-TOF MS, and ESI tandem MS/MS. The olefin/CO2-derived materials depolymerized by hydrolysis at 80 °C in 1 M NaOH. This method and the observed chemical structures expand the materials and properties that can be obtained from carbon dioxide and olefin feedstocks.