Liquid droplets are released in the concave‐wall jet to investigate their deformation and breakup characteristics. CCl4 and water are the dispersed and continuous phases. The study reveals that the three modes of single droplets in the concave‐wall jet are non‐breakup, binary breakup, and multiple breakup. When the Weber (We) number is less than 30, the mode of binary‐breakup is primary for the droplets, however, there are only multiple‐breakup modes when We > 47. The non‐breakup and binary‐breakup modes are beneficial to the gravity and centrifugal separation because of little deformation and high axial velocity of the droplet. Effects of continuous‐phase tangential velocity and shear rate distribution on the droplet image sequence are studied. Droplet breakup occurs mainly in the region of high shear rate.