Polyether secondary amines with polyoxyethylene ether and long-chain alkyl, have been widely used as pigment dispersing agents due to their adjustable structure, low toxicity, and good dispersibility. At present, polyether secondary amines are mainly synthesized via the reaction between polyether polyol and liquid ammonia with low yield and harsh condition. Herein, bis(C12-14 alkyl polyoxyethylene) secondary amine (S/C12-14E5) was successfully synthesized via the intermolecular deamination coupling of amine-terminated polyether with C12-C14 alkyl group (A/C12-14E5) under ambient pressure. The influences of coupling temperature, catalyst dosage, hydrogen flow rate and reaction time on the selectivity of S/C12-14E5 were systematic studied. The results showed that the average secondary amine content reached up to 97.3% when the conditions of reaction temperature was 200 ℃, the amount of catalyst was 2.5% based on the total mass of raw material, the hydrogen flow was 200 mL/min, and reaction time was 5 h. On this basis, we studied the substrate scope and scale-up reaction to demonstrate the utility of our protocol. A possible reaction mechanism was also proposed.