A new polymerized monomeric reactant (PMR)-type polyimide, designated TriA X, was investigated to determine polymer structure, processability, thermal, and mechanical properties and establish the relationship between the molecular structure and those properties. TriA X is a PMR-type polyimide with an asymmetric, irregular, and nonplanar backbone. Both the imide oligomers and the cross-linked polyimides of TriA X exhibited loose-packed amorphous structures, independent of thermal processing. The peculiar structures were attributed to the asymmetric backbone, which effectively prevented the formation of closed-packed chain stacking typically observed in polyimides. The imide oligomers exhibited a lower melt viscosity than a control imide oligomer (symmetric and semi-crystalline), indicating a higher chain mobility above the glass transition temperature ( Tg). The cured polyimide exhibited a Tg = 362°C and a decomposition temperature = 550°C. The cross-linked TriA X exhibited exceptional toughness and ductility (e.g. 15.1% at 23°C) for a polyimide, which was attributed to the high-molecular-weight oligomer and loose-packed amorphous structure. The thermal and mechanical properties of TriA X surpass those of PMR-15 and AFR-PE-4.