The formation of a charge transfer exciton(CTE) has been shown to be a crucial intermediate step in the charge separation process of efficient OPV cells.The photoluminescence quantum yield of CTE is about two orders of magnitude less as compared to singlet excitons from the organic donor, but photovoltaic efficiency is still adversely affected by its recombination. Although the charge generation through CTE and its impact on solar cell performance has been studied extensively, the process of recombination of CTE has not been completely addressed yet. Most of the polymer blends used in OPV showspontaneous emission from the lowest lying CT state in the near infra-red (IR) range 0.8 eV- 1.6eV. Here we report the stimulated emission (SE) from the hot CTE from the blend of PCBM and electron-donating polymer poly [naphtha [2,1-b: 3,4-b′] dithiophene–4, 7-di (thiophen-2-yl)benzothiadiazole] (PNDT–DTBT) at probe energy 1.66 eV close to the singlet emission energy of the organic donor. This was observed preferentially in the face on configuration of the bulk heterojunction with cross polarization of pump and probe, which was obtained when the fluorinated PNDT-DTBT was blended with PCBM in dichlorobenzene.We did not observe the SE from neat PNDT-DTBT and neat PCBM on that configuration of pump and probe, confirming that the SE is from interface excitons. Polarization anisotropy measurements, we were able to isolate hot CTE emission from singlet donor emission.