Highly photoluminescent and air-stable AgInS2 quantum dots (AIS QDs) were synthesized by a hot-injection route in N2 atmosphere and dark environment. The as-synthesized AIS QDs were further capped with ZnS shell by one-pot method in order to enhance the photoluminescence (PL) intensity. The photo-electronic property and the morphology of AIS QDs and AIS/ZnS QDs were characterized by ultraviolet-visible spectroscopy (UV), PL spectroscopy and transmission electronic microscopy (TEM). The results indicated that the narrow and symmetrical PL spectra of AIS QDs was time-dependent, and the emission wavelength of AIS QDs could be tunable within 436–610 nm by altering the initial Ag/In ratios. After being capped with ZnS shell, the AIS QDs showed excellent optical characteristics, including PL QYs up to 15%. The TEM results indicated that the spherical AIS/ZnS QDs were nearly monodispersed and homogeneous with an average particle size of 8 nm. The heavy metal free and high luminous AIS/ZnS QDs have great potential in biological application.