In order to investigate the optical breakdown and plasma distribution during the interaction between ultrashort laser pulses and double droplets, based on the nonlinear Maxwell’s equations and the ionization rate equation, a transient coupled model of femtosecond laser and double droplets was constructed by finite element analysis. The free electron density and laser field distribution of micron-sized double droplets irradiated by femtosecond laser were calculated, and the effects of double-droplet structures on droplet optical breakdown and plasmonic changes were obtained. The results show that the breakdown threshold of the second droplet is approximately 35% of that of a single droplet under the same conditions. The plasma morphology and the location of the breakdown point vary with the distance between the double droplets, and a nanoplasma jet is generated in focused region. In addition, the absorption of laser energy by the second droplet decreases with increasing distance between the double droplets. The energy absorption of the double droplets is about 3% of that of the single droplet when incident with both laser intensity satisfying their breakdown threshold. The absorption of laser energy by the second droplet increases with the increase of laser intensity, and the energy absorption ratio eventually tends to 0.01, which is only 1.5% of that of a single droplet. The investigation provides a certain reference for laser-induced water breakdown and the transmission of laser in the atmosphere.