While molecular weight distribution (MWD) is one of the most important properties of soluble microbial products (SMPs), mechanisms underlying effects of MWD of SMPs on membrane fouling have not well unveiled. In this study, it was found that, the supernatant of sludge suspension in a membrane bioreactor (MBR) for wastewater treatment can be fractionated into a series of SMPs samples with different molecular weight (MW) fraction. The real gel sample mainly formed by the rejected SMPs on membrane surface had a high specific filtration resistance (SFR) of 1.21 × 10¹⁶ m⁻¹ kg⁻¹. The SFR of SMPs samples and the model foulants of polyethylene glycol (PEG) increased with their MW. The change trend of SFR with MW cannot be sufficiently explained by three-dimensional excitation-emission matrix (EMM) and chemical compositions. Tyndall effect analysis indicated that gelating ability of SMPs and PEG in the solution increased with their MW. Scanning electron microscope (SEM) confirmed gel structure changes with the PEG MW. Accordingly, mechanisms based on Carman–Kozeny equation and Flory–Huggins lattice theory were proposed to interpret SFR of SMPs with low and high MW, respectively. Simulating these two mechanistic models on PEG samples resulted in the comparable SFR data to the experimental ones, indicating the correctness and feasibility of the proposed mechanisms. The proposed mechanisms provided in-depth understanding of membrane fouling regarding MW, facilitating to develop effective membrane fouling mitigation strategies.