A review of experimental and theoretical studies performed over the past three decades on high pressure chemistry of solid CO2, at 0-80 GPa and 40-3000 K, is presented. Emphasis is placed on the recently discovered non-molecular covalent crystalline phase V, and its glassy counterpart a-CO2, along with other molecular phases, whose interpretation is crucial for determining the reaction path to non-molecular CO2. The matter is still under debate, and many open issues are outlined, such as the true reaction mechanism for forming phase V. Finally, we propose arguments to stimulate possible future research in a more extended P-T range. This work is a tutorial review and should be of general interest both for solid state chemistry and condensed matter physics communities.