We report the investigation of third order optical nonlinearity of 2,4,6-tri-(p-hyptoyoxylphenyl) pyrilium tetraborate doped PMMA using nanosecond laser pulses at 532nm wavelength by employing Z-Scan technique. To see the effect of polymer host, the results have been compared with the pure dopant. The material shows a large negative nonlinearity with real and imaginary parts of χ (3) are -3.31x10 -14 esu and 0.73x10 -14 esu respectively. Excited state absorption cross-section is found to be 3.41x10 -48 cm 4 .s/photon in PMMA host. The magnitude of third order nonlinear parameters increases when the compound is doped into PMMA matrix because of change in the conformation of chain geometry as a result of charge transfer processes. The values are comparable with a best known nonlinear liquid crystal molecule namely, 4-cyano-4'-n-pentylbiphenyl in the nematic phase. Hence, these molecules can be suitably used as nonlinear optical materials in PMMA matrix for device applications.