Economically feasible production of conventional bioenergies such as biofuels, biopower and bioheat is a challenge in biorefineries because they have to compete with inexpensive fossil fuel energies while external production costs are rarely included into the present-day policies. Biomass consists of unique complex chemical structures that cannot be easily artificially synthesized and may be beneficially employed in varidus practical applications. Therefore, strategies relying on complete biomass disintegration through combustion, gasification or fermentation only to simple usable bioenergies do not lead to optimal utilization of biomass feedstock. Instead, cascading approaches are required in order to maximize biomass valorization. Conseqtiently, high value low-volume bioproducts coupled to bioenergies with potential to improve economic viability of biorefineries and biomass resource utilization are urgently required. Integrated production of bioenergies and bioproducts may be achieved by coupling existing biofuel plants with hew bioindustries, by retrofitting existing bioindustries with new bioenergy facilities or by erecting completely new integrated facilities. The current paper reviews literature and provides systematized insights into various high-value low-volume bioproducts coupled to bioenergies in biorefinery contexts. It analyses potential benefits of a range of such bioproducts and gives comments on associated business development. The review thus creates foundations for more thoughtful design procedures of economically feasible sustainable biorefineries that could meet technical and market requirements and improve cascading biomass utilization. Owing to insufficient technology readiness the study also aims at improved understanding of major technological gaps limiting expanded economically viable utilization of high-value bioproducts through biorefineries. It is emphasized that the major advantage of biorefineries is their suitability for maximizing valorization of structural and energetic potentials lying in biomass. The study suggests that new business models introducing high-value bioproducts to biorefineries are essential for achieving economic viability of industries within bioeconomy.