Ionic liquid (IL) materials are promising electrolytes with striking physicochemical properties for energy and environmental applications. Heterogeneous structures and transport quantities of monomeric and polymeric ILs are intrinsically intercorrelated and span multiple spatiotemporal scales, which is more feasible for coarse-grained (CG) simulations than atomistic modelling. Herein we constructed a novel CG model for ethyl-imidazolium tetrafluoroborate ILs with varied cation alkyl chains ranging from C₂ to C₂₀, and the interaction parameters were validated against representative static and dynamic properties that were obtained from atomistic reference simulations and experimental characterizations at relevant thermodynamic states. This CG model was extended to study thermotropic phase behaviors of monomeric ILs and to explore ion association structures and ion transport quantities in polymeric ILs with different architectures. A systematic analysis of structural and dynamical quantities identifies an evolution of liquid morphology from homogeneous to nanosegregated structures and then a smectic mesomorphism via a gradual lengthening of cation alkyl chains, and thereafter a distinct structural transition characterized by a monotonic decrease in orientational and translational order parameters in a sequential heating cascade. Backbone and pendant polymeric ILs exhibit evident anion association structures with cation monomers and polymer chains, and striking intra- and interchain coordinations between cation monomers owing to an intrinsic polymer architecture effect. Such a peculiar ion pairing association leads to a progressive increase in anion intrachain hopping probabilities, and a concomitant decrease in anion interchain hopping events with a gradual lengthening of polymeric ILs. The anion diffusivities in polymeric ILs are intrinsically correlated with ion pairing association lifetimes and ion structural relaxation times via a universal power law correlation D ∼ τ⁻¹, irrespective of polymer architectures.