Abstract Bio‐based 2,5‐furandicarboxylic acid (FDCA) can be used to produce poly(ethylene 2,5‐furandicarboxylate) (PEF), which has a great potential for barrier packaging, and so forth. Herein, the first two steps of the esterification reaction of FDCA with ethylene glycol (EG) were investigated. The dissolution rate of FDCA in EG is fast, the solubility of FDCA in EG and monohydroxyethyl 2,5‐furandicarboxylate (MHEF) reaches 159.12 and 489.84 g kg −1 at 180 °C, respectively. The initial esterification of FDCA with EG to form MHEF is a zero‐order reaction ( k 1 = 266.77 × 10 −3 mol kg −1 min −1 ) with an activation energy of 114.52 kJ mol −1 ; the esterification of MHEF with EG to form bis(hydroxyethyl) 2,5‐furandicarboxylate (BHEF) is a first‐order reaction ( k 2 = 9.72 × 10 −3 min −1 ) with an activation energy of 86.12 kJ mol −1 . These results identified accurate parameters for the dissolution and esterification processes of FDCA in EG, which provide important guidance for the polymerization of FDCA polyesters.