The power law ηrel ∼ Ca of maltodextrins with higher entanglement concentrations (Ce) of dextrose equivalent (DE) 4, 10, and 18 exhibits an unusually high exponent a, ranging from 10.34 to 14.38 in congested solutions where particles occupy significant space. This contrasts with the dilute exponents (a ∼2) typically observed in polymer–solvent systems. To address this issue, several viscosity factors were evaluated using the Einstein–Roscoe and Mooney equations, which demonstrated viscosity dependence due to volume fraction (ϕ) > 0.35, shape, crowding factor (k) packing factor (1/k∼0.5) and centered cubic cell (CC), particularly for larger chain sizes (>20 glucoses) in DE-4. Chain electrical charges significantly stiffen the chain and increase its length beyond the theoretically predicted Kuhn persistent length (Lp), which seems to be responsible for the exponential increase in viscosity. Normalizing the viscosity/charge data revealed a log–log plot consistent with the exponent a of the general power law theory. In addition to concentration, electrospinning processing is influenced by strong particle–particle charge interactions, (ϕ), packing factor (1/k), CC, and chain sizes. The Maxwell model demonstrated poor interaction for DE-4 (modulus ∼286 Pa at maximum ϕ due to loose packing of CC, in contrast to DE-18, which exhibited a modulus of 994 Pa for a solution with maximum ϕ> 0.5 and a congested solution of 52% w/v, packing factor of 0.68, and high particle–particle interaction of the body-centered cubic (BCC) cell, favoring electrospun fiber formation. The packing factor, ϕ, and cell type, are highly sensitive and have potential applications in food systems, 3D bioprinting, among many other scientific domains.