This mini-review assesses supercritical carbon dioxide (scCO2) extraction and high-pressure carbon dioxide pre-treatment technologies for valorisation of corn stover agricultural residues with particular focus on showing how these can aid in the creation of a holistic biorefineries. Corn stover is currently the largest source of agriculture residues in the USA, as such there is significant potential for exploitation to yield valuable chemicals. ScCO2 extraction could lead to the recovery of a variety of different chemicals which include flavonoids, sterols, steroid ketones, hydrocarbons, saturated fatty acids, unsaturated fatty acids, fatty alcohols, phenolics and triterpenoids. Importantly, recent studies have not only demonstrated that supercritical extraction can be utilized for the recovery of plant lipids for use in consumer products, including nutraceuticals and personal care, but the processing of treated biomass can lead to enhanced yields and recovery of other products from biorefinery processes. Despite the great potential and opportunities for using scCO2 and high-pressure systems in a biorefinery context their real-world application faces significant challenges to overcome before it is widely applied. Such challenges have also been discussed in the context of this mini-review.