A novel approach based on the preceramic paper method was used for the fabrication of Ti3SiC2-based material. Elemental powders of Ti, TiC, Si, C, and organic additives were used as starting materials. The Rapid Köthen process was used to fabricate the preceramic papers. The high-loaded green body of preceramic papers was heat-treated up to varying temperatures of 1300, 1400, 1500, and 1600 °C for 1 h in an Ar atmosphere. By using an excess amount of Si powder in the basic composition, the amount of Ti3SiC2 in the sintered specimen could be increased while the amount of TiC could be reduced. X-ray analysis showed that the paper-derived sample with the basic powder composition 3Ti/3TiC/3Si/C was a single phase within the resolution limit of the instrument used. The high purity of Ti3SiC2 can be explained by the partial formation of amorphous C which could not be detected by X-ray diffraction. Scanning electron microscopy analysis of fracture surfaces showed the characteristic lamellar structure of the paper-derived MAX phase.