The effects of solvents on the conformation of hemin and their implications on the dynamics of the complex have been studied using the time-resolved optical Kerr effect (OKE) with 35 fs laser pulses (at a central wavelength of 800 nm). The OKE enabled estimation to be made of the third-order nonlinear electronic susceptibility (χ(3)) of hemin solutions: it was found to be significantly smaller than that in hemin thin films. The real and imaginary components of χ(3) were negative in both the solvents, suggesting that one-photon as well as two-photon absorption processes contribute to the nonlinear electronic susceptibility of hemin. Our study of the ultrafast heme dynamics not only unveils the instantaneous electronic response related to electronic susceptibility but also brings to the fore a novel libration process that has hitherto remained undetected. The hindered rotation in the femtosecond domain that may be responsible for this libration process possibly stems from π-π hemin oligomers formed in aqueous solution. The present results provide new insights into the conformational dynamics in the self-assembly of heme oligomers that may also be significant in certain pathogenic conditions where free heme is formed in biological systems.