Herein, two water-soluble PROXYL-based magnetic resonance imaging (MRI) macromolecular organic contrast agents (mORCAs) are designed and synthesized: linear and cross-linked PCE-mPEG-Ppa-PROXYL. They are prepared by conjugating linear and cross-linked poly(carboxylate ester) (PCE) with poly(ethylene glycol) (mPEG2000)-modified nitroxides (PROXYL), respectively. Both mORCAs form self-assembled aggregates in an aqueous phase and PROXYL is protected inside a hydrophobic core to achieve great resistance to reduction in the physiological environment, and they have low toxicity. Since cross-linked PCE-mPEG-Ppa-PROXYL possess a branched architecture, its self-assembled aggregate is more stable and compact with a greater particle size. Cross-linked PCE-mPEG-Ppa-PROXYL outperform the linear one in the following aspects: 1) its longitudinal relaxivity (r1 = 0.79 mm -1 s-1) is higher than that of the linear one (r1 = 0.64 mm -1 s-1) and both excel the best mORCA reported so far (r1 = 0.42 mm -1 s-1); 2) its blood retention time (≈48 h) is longer than that of its linear counterpart (≈10 h); 3) cross-linked PCE-mPEG-Ppa-PROXYL provided better MR imaging contrast resolution in normal organs (liver and kidney) and tumor of mice than the linear one. Overall, cross-linked PCE-mPEG-Ppa-PROXYL may have great potential to be a novel metal-free macromolecular contrast agent for MR imaging. © 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.