Quaternary Cd-Cu-Fe-S nanocrystals (NCs) exhibiting a strong size tunable photoluminescence were synthesized for the first time by tuning the reaction temperature from 120 °C to 210 °C. The preparation procedure involved cadmium acetate, copper acetate, iron chloride, and sulfur powder dissolved in oleylamine as precursors. The wavelength of the emission can be tuned from 640 nm to nearly 1000 nm by only changing the size of the as-prepared NCs from 3.0 nm to 15 nm. Interestingly, these NCs possess a relatively high quantum yield of over 57% without coating any wide band-gap shell materials. The study on the optoelectronic properties of Cd-Cu-Fe-S NCs, where an order of photocurrent was enhanced under AM1.5 illumination, demonstrated their suitability as optically active components to fabricate optoelectronic devices.