A new class of biodegradable cationic macromolecules for DNA binding and condensation was developed by end‐group‐functionalization of poly(trimethylene carbonate). A series of one‐ and two‐armed structures was synthesized and their interaction with DNA was evaluated. To aid data interpretation, a non‐linear modeling method was applied to show efficient DNA binding that was intimately related to cationic charge density and macromolecular architecture. One‐armed, low charge density structures were consistently found to bind to DNA at lower charge ratios than their two‐armed, high charge density counterparts. This suggests that polymer backbone structure and characteristics are important considerations in the development of efficient cationic polymer systems for DNA condensation and delivery.