Four types of organofunctionalized (by phenyl, 3-aminopropyl, 3-chloropropyl, and N-aminoethylaminopropyl, respectively) mesoporous silicates MCM-41 (hereafter R-MCM-41) have been successfully synthesized via the grafting method, the conventional templated sol-gel technology, and the original stepped templated sol-gel technology. The prepared inorganic-organic hybrid materials were characterized in detail by powder X-ray diffraction (XRD), Si-29 and C-13 MAS NMR spectrometry, isothermal nitrogen adsorption-desorption analysis, FT-IR spectrometry including in situ drift technique, and thermogravimetric analysis (TGA). Through a series of investigations and comparisons, the advantageous stepped templated sol-gel technology introduced in this paper is demonstrated to be a remarkable approach that gathers the superior properties of the current grafting method and the conventional hydrothermal co-condensation synthesis, yielding as a consequence both thermodynamically firm fixation and relatively large content of organic functional species on the MCM-41 support. The novel synthetic strategy also evidently shortens the crystallization time for the organofunctionalized MCM-41 with regular specific structure.