Mechanical properties enhancement of ceramic tiles by a simple coating technique using polyurea was investigated. Solventless polyurea coatings were employed. The effect of coating sides of the ceramic substrate and film thickness on the mechanical properties were examined in three-point bend tests. The back-coated ceramic tile demonstrated a significant improvement in bending strength (by 25–50%) as compared to the top-coated one. The stress distribution in the substrate was analyzed by the finite element method, and the mechanism of improving mechanical properties was discussed. Based on FEM analysis, the polyurea back-coating appeared to be more effective as regards the stress distribution. The stress distribution in the back-coated ceramic tile is more uniform due to the cushioning effect of the supporting pins. The mechanism of the polyurea coating effect was evaluated in the experiment and finite element analysis. It was established that the stress distribution due to the polyurea coating was of importance for the improvement of the bending strength of substrates.