Charge carrier dynamics of multinary quantum dots like CuInS 2 (CIS) nanocrystals (NCs) is not clearly understood, especially in ultrafast time scales. Herein we have synthesized colloidal CIS NCs that show defect-induced emission between donor (antisite) and acceptor (internal/surface) states as indicated from steady-state and time-resolved photoluminescence (PL) measurements. Subpicosecond transient absorption (TA) spectra of CIS NCs reveal a gradient of electronic states that exists above the conduction band edge. The electron cooling rate has been determined to be ∼0.1–0.15 eV/ps. The cascade of electron cooling dynamics was monitored after following the TA kinetics at different electronic states. Interestingly, the kinetics at the antisite state unveil a biexcitonic feature, which has been enlightened through a probe-induced biexciton mechanism. With progressively higher fluence (⟨N⟩), the biexciton binding energy increases, and the electron cooling to the antisite state considerably slows down. Extra energy released during Auger recombination of bi/multiexcitons are used to re-excite the electron to a further high energy level, resulting in longer electron cooling time to the antisite states.