Multiexciton harvesting from semiconductor quantum dot has been a new approach for improving the semiconductor device efficiency which include quantum dot sensitized solar cells (QDSC) and photodetectors. Till date, not many reports are available where relation between exciton/multiexciton dissociation in metal−semiconductor nanohybrid system and boosting the power conversion efficiency (PCE) of QDSC are discussed. Herein we report a detailed spectroscopic investigation on the dissociation dynamics of i) exciton in Au@CdSe, ii) biexciton in Au@CIS (CuInS₂) and, iii) trion in Au@2D-MoS₂ utilizing both time-resolved PL and ultrafast transient absorption (TA) techniques. Ultrafast transient absorption studies suggest that in all the above three systems the ultrafast formation of exciton/bi-exciton/trion, which efficiently dissociates in Au-semiconductor nano-hybrid structures. Prior to the dissociation electrons are captured by Au NP in the nanohybrid from the conduction band of CdSe/CIS/2D-MoS₂ nano-structures which is energetically higher than Fermi level of Au. Here we demonstrate the proof-of-concept in multi-electron dissociation which may provide a new approach for improving the efficiency in QDSSCs. These findings can be an efficient approaches towards the design and development of efficient solar cell and optoelectronic devices using the principles of multiexciton/trion generation and extracting them in metal-semiconductor nanohybrid system.