This paper reports the linear and third-order nonlinear optical (NLO) properties of chlorophyll-a, a natural pigment extracted from the medicinal plant Andrographis paniculata. Silica column chromatography technique was used to extract the chlorophyll-a from the plant leaves. The functional groups present in the extracted sample were recognized by Fourier transform infrared (FT-IR) spectra. The sample was also characterized by UV–Vis, fluorescent spectra and Z–scan techniques. Z–scan study reveals that the extracted natural pigment chlorophyll-a evinces a large negative nonlinear refractive index n2 and nonlinear absorption coefficient β respectively owing to self-defocusing and saturable absorption behaviors. Third-order NLO susceptibility χ(3) of chlorophyll-a was measured to be of the order of 10–6 esu. The sample fulfilled the conditions for figure of merit and we believe that the natural pigments extracted from the Andrographis paniculata leaves may be suitable for all-optical switching applications.