Partially bio‐based triepoxides, 1,3,5‐tri‐O‐methyl‐2,4,6‐tri‐O‐(oxiran‐2‐yl‐methyl)‐myo‐inositol (4) and 2,4,6‐tri‐O‐(oxiran‐2‐yl‐methyl)‐myo‐inositol 1,3,5‐orthoacetate (5), were synthesized from naturally occurring myo‐inositol. These two triepoxides differ from each other in terms of rigidity of the core structure; while the former triepoxide has a more flexible cyclohexane core, the latter has a highly rigid adamantane‐like orthoester core. Triepoxide 5 readily reacted with nucleophilic monomers such as diamines, dithiol, and trithiol to yield networked polymers. The glass transition temperatures (Tgs) of these polymers were higher than those of comparable networked polymers obtained by the polyaddition of triepoxide 4 with the same nucleophilic monomers, implying that the rigidity of the orthoester moiety contributed to the efficient restriction of the polymer chain in the synthesized networked polymers.