Infrared transient absorption (IRTA) spectra for excitons and biexcitons in CuCl bulk crystal have been measured by pump‐probe spectroscopy. The IRTA peak energy of the exciton agrees with the transition energy between Rydberg 1s to 2p states reported in one‐ and two‐photon absorption measurement. On the other hand, the IRTA peak energy of the biexcitons locates in energy higher than that of the excitons, which is reasonable by taking hydrogen molecule model into account. In addition, our results support the enhancement of the transition energy between 1s and 2p states in quantum dots compared to the bulk case. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)