5-Demethylnobiletin (5-DMN), identified in the aged citrus peels, has received increasing attentions due to its outstanding bioactivity among citrus polymethoxyflavones (PMFs). However, the poor water solubility and high crystallinity limit its oral bioavailability. Besides, the solubility of 5-DMN in the oil is very limited, which restricts its loading capacity in emulsions for bioavailability enhancement. In this study, an organogel formulation was developed to improve the solubility of 5-DMN in medium-chain triacylglycerols by 3.5 times higher without crystal formation during 5-day storage at room temperature. Increasing the gelator (i.e., sugar ester) concentration led to the increase of viscosity and a gel-like structure of the organogel. The ternary phase diagram of organogel-based emulsions was explored, and 40% organogel was selected as the oil phase for emulsion preparation. Increasing the concentration of Tween 80 from 0% to 6% decreased the droplet size and viscoelasticity of the emulsions. Two in vitro models, the pH-stat lipolysis model and TNO gastro-intestinal model (TIM-1), were applied to investigate the bioaccessibility of 5-DMN in different delivery systems. Compared with the conventional emulsion and oil suspension, the pH-stat lipolysis demonstrated that the organogel-based emulsion was the most efficient tool to enhance 5-DMN bioacccessibility. Moreover, TIM-1 digestive study indicated that 5-DMN bioaccessibility delivered by organogel-based emulsions was about 3.26-fold higher than that of oil suspension. Our results suggested that the organogel-based emulsion was an effective delivery route to enhance the loading and bioaccessibility of lipophilic compounds of high crystallinity.