The structural and electronic properties of an excess electron (EE) in the ionic liquid (IL) 1-methylpyridinium chloride were explored using ab initio molecular dynamics simulations and quantum chemical calculations to give an overall understanding of the solvation and transport behavior of an EE in this IL.The results show that the EE resides in cation π*-type orbitals and that the electronic states can be characterized by the alternating appearance of localized and delocalized states during the time evolution.