The invention discloses a porous rapid combustion bio-combustible substance particle and a preparation process thereof. The particle comprises, by weight, 40-50 parts of corn straws, 30-40 parts of wheat straws, 22-30 parts of cotton seed hulls, 18-24 parts of peanut hulls, 25-35 parts of bagasse, 16-20 parts of edible fungi residue, 8-12 parts of activated kaolin, 13-17 parts of gamma-aluminum oxide, 16-20 parts of ammonium bicarbonate, 10-14 parts of polyacrylamide and 1-3 parts of kindling agents. The preparation process of the particle includes the steps: S1 crushing biomass materials, soaking the crushed biomass materials by ammonium hydroxide, and exploding soaked biomass materials by steam; S2 mixing and expanding the biomass materials, the activated kaolin, the gamma-aluminum oxide, the ammonium bicarbonate and the polyacrylamide, performing press forming on the mixed and expanded materials, roasting the formed materials at the temperature of 150 DEG C until the porosity of a green body reaches 20-25%, and spraying the kindling agents. According to the particle, the biomass materials are treated by combining an ammonium hydroxide soaking technology and a steam explosion technology, inner gaps of the biomass materials are enlarged, an irregular porous structure is formed by the aid of thermal decomposition reaction between the ammonium bicarbonate and the polyacrylamide,and complete combustion of fuels is facilitated.