Elasto-inertial turbulence (EIT), a new turbulent state found in polymer solutions with viscoelastic properties, is associated with drag-reduced turbulence. However, the relationship between EIT and drag-reduced turbulence is not currently well-understood, and it is important to elucidate the mechanism of the transition to EIT. The instability of viscoelastic fluids has been studied in a canonical wall-bounded shear flow to investigate the transition process of EIT. In this study, we numerically deduced that an instability occurs in the linearly stable viscoelastic plane Couette flow for lower Reynolds numbers, at which a non-linear unstable solution exists. Under instability, the flow structure is elongated in the spanwise direction and regularly arranged in the streamwise direction, which is a characteristic structure of EIT. The regularity of the flow structure depends on the Weissenberg number, which represents the strength of elasticity; the structure becomes disordered under high Weissenberg numbers. In the energy spectrum of velocity fluctuations, a steep decay law of the structure’s scale towards a small scale is observed, and this can be recognized as a ubiquitous feature of EIT. The existence of instability in viscoelastic plane Couette flow supports the idea that the transitional path toward EIT may be mediated by subcritical instability.