Based on orthogonal experimental design, the key solidification controlling technology of Solidified/Stabilized (S/S) sludge with high total organic content (TOC) by cement, lime and metakaolin was explored by macroscopic tests, chemical components measurements and microscopic analysis. The macroscopic tests show that, the permeability coefficient is mainly affected by initial water content and lime content, and the unconfined compression strength is mainly affected by cement content and lime content. The chemical components measurements show that, the solidification effect of S/S sludge with high TOC is controlled by organic matter consumption, and organic matter consumption is determined by the alkaline environment from the cement and lime hydration reactions, which is mainly affect by the initial water content and lime-metakaolin content ratio. The microscopic analysis results show that, lime consumes parts of organic matter while excess lime produces weak Ca(OH)2 crystal fluffy sheet structure, matakaolin produces pozzolanic reactions with cement and lime instead of soil particles, and consumes the weak Ca(OH)2 crystal fluffy sheet structure produced by superfluous lime. The research has confirmed key controlling points of S/S sludge in case of high TOC, which will provide theoretical guidance and technical support for S/S sludge promotion with high TOC.