Silver indium sulfide (AIS) quantum dots (QDs) with different Ag/In molar ratios were synthesized via a hot-injection method. Intense photoluminescence (PL) originating from the donor–acceptor pair recombination were observed for all the samples and the emission peak blue-shifted from 739 to 632nm, being similar to the behavior of the absorption onset as the Ag/In ratios decreased. The highest PL quantum yield (QY) of the obtained ternary AIS QDs was ca. 62% with an optimum ratio of Ag/In=1/4. Compared with AIS QDs, when Zn ions were introduced, the absorption spectra of the obtained quaternary Ag–Zn–In–S QDs were blue-shifted, and their emission peaks moved to higher energies accordingly, showing a tunable emission from red to green by altering the band gap energy. In order to further study the electroluminescence (EL) as well as looking forward to the applications in the optoelectronic devices of the obtained highly luminescent nanoparticles, the colloidal AIS QDs were deposited as thin films to the sandwich-like structured QD-LED. The experimental results showed that the obtained EL device exhibited EL emission originated from QDs thin films by adjusting the turn on voltage, which is for the first time to realize EL of AIS QDs in such QD-LED.