Cross-linked silicone elastomers constructed with dynamic-covalent boronic esters are first synthesized by photoinitiated radical thiol-ene click chemistry. The resultant samples can be cut with a sharp knife into two pieces and then healed via the reversibility of the boronic ester cross-linkages to restore the original silicone sample within 30 min. Regulation of luminescent properties is achieved by incorporating organic dye into the elastomers through a one-pot thiol-ene reaction. The proposed synthesis procedure demonstrates a new strategy to produce boronic acid silicone materials capable of self-healing without external forces.