Gear wear is one of the most common gear failures, which changes the mesh relationship of normal gear. A new mesh relationship caused by gear wear affects meshing excitations, such as mesh stiffness and transmission error, and further increases vibration and noise level. This paper aims to establish the model of mesh relationship and reveal the vibration characteristics of external spur gears with gear wear. A geometric model for a new mesh relationship with gear wear is proposed, which is utilized to evaluate the influence of gear wear on mesh stiffness and unloaded static transmission error (USTE). Based on the mesh stiffness and USTE considering gear wear, a gear dynamic model is established, and the vibration characteristics of gear wear are numerically studied. Comparison with the experimental results verifies the proposed dynamic model based on the new mesh relationship. The numerical and experimental results indicate that gear wear does not change the structure of the spectrum, but it alters the amplitude of the meshing frequencies and their sidebands. Several condition indicators, such as root-mean-square, kurtosis, and first-order meshing frequency amplitude, can be regarded as important bases for judging gear wear state.