The study of structural defects in particle systems is of great value for studying solid-liquid melting. The volume fraction is a key parameter that can be used to accurately quantify the phase-transition process. The collective behavior and interaction form in a wet particle system are much more complex than that of a dry particle material because of the existence of liquid bridge force between the wet particles. In this paper, the structural defects and the critical value of solid-liquid transformation in the monolayer wet particles during solid-liquid melting under vertical vibration are experimentally studied. The contact model of the wet particle system is constructed according to experimental and theoretical analysis, and the structural changes of the particles in the melting process of the quasi-two-dimensional wet particle system are quantified. The Voronoi tessellation is established to study the phase transition of the particle system, and the local volume fraction is adopted to determine the state of structural defect change during melting. The experimental results indicate that the phase-transition process is caused by structural defects in the solid. The defects appear from the edge of the particle system, and the chain defect pairs spread to the center. The reason for structural defects at the edge of the cluster is that the particles at the edge of the cluster are subjected to less liquid bridge force, and the kinetic energy brought by the collision between the particles and the bottom wall makes the particles become active and begin to explore the available space. The chain defects are caused by the force chain generated by the fluid bridge force, which makes the particles tend to move together in rows. In addition, the local volume fraction of seven-phase defective particles decreases significantly and is much smaller than that of five-phase defective particles and six-phase defective particles when defects occur. Therefore, the evolution and the critical state of the structural defects can be quantified by measuring the change in the minimum local volume fraction (the local volume fraction of particles with 7-fold defects) in the particle system. The local volume fraction of the analysis shows that when the minimum local volume fraction ϕ ≤ 0.6652 defects occur, and when ϕ ≤ 0.4872 particle system transforms from solid to liquid.