The invention provides a method for producing high calorific value syngas by using industrial byproducts, which contains iron, calcium, magnesium, silicon, aluminum. The composition can replace tradition bed material in fluidized bed reactor as catalysts to improve the energy conversion efficiency. Industrial by-products are doped with phosphorus or boron to control the electron polarization on the surface of the catalyst (dipole moment). Therefore, the charge characteristics on the surface of the catalyst can be modified. The catalysts can be applied into a fixed bed, fluidized bed or entrained bed gasifier to reduce the activation energy of the gasification reaction at 600-1000 ℃ and conversion hydrocarbons into syngas. The method of the invention uses inexpensive industrial by-products to synthesize catalytic bed materials, which not only enhances the gasification efficiency but also expands the application of by-products to improve the economic competitiveness of the gasification process.