In liquid−liquid contact process, the motion of droplets relative to the surrounding fluid always involves accelerating and decelerating, which affects the mass, heat, and momentum transfer. The lack of experimental data of the unsteady drag coefficient has been one of the limitations on the prediction of the unsteady flow field. In this study, the accelerated and decelerated water droplets in an organic phase were measured by a high-speed camera. The results show that with a decrease in droplet diameter, the acceleration becomes more significant, while the absolute relative velocity decreases, causing a lower Reynolds number. The Basset force and add mass force were solved numerically and compared with drag force. The unsteady drag coefficient is always smaller than the corresponding steady drag coefficient in the case of accelerating relative flow and larger than that in the case of decelerating relative flow. A new unsteady drag coefficient model has been established, which has an acceptable agreement with the experimental data.