Two organogelators of different chemistry (a fatty acid derivative and a bis-urea derivative), as well as their blends, were used to impart shape stability to a bio-based phase-change material (PCM) bearing a near-ambient phase-transition temperature. Characterization of the individual gelators and their blends revealed their ability to immobilize the PCM by forming a continuous fibrillar network. The fibrils formed by the fatty acid derivative were helical, while the bis-urea derivative formed smooth fibrils. Also, the bis-urea derivative formed a continuous network at a lower critical concentration than the fatty acid derivative. At each fixed concentration, the bis-urea derivative yielded gels with higher thermal stability than the fatty acid derivative. The two gelators blended in certain ratios demonstrated a strong synergistic effect, providing gels with a significantly higher modulus (∼20-fold) and yield stress (∼1.5-fold) than each gelator individually. PCM gelation did not significantly affect its thermal behavior, however, affected its crystalline morphology. The gelled PCM displayed stacked structures, consisting of alternating pure PCM layers separated by layers formed by gelator fibrils. The phase diagram of the triple system comprising both gelators and PCM demonstrated either single or double gelation behavior depending on the composition. These findings may provide guidelines for the development of novel, shape-stable PCMs, which could be of potential use in various thermal energy storage applications.