The invention discloses a composite solid base catalyst which is mainly prepared from the following components in parts by mass: 100 parts of gamma-Al2O3 as a carrier, 0.5-5 parts of a binding agent as a loaded component, 1-25 parts of a magnesium-containing compound, 1-25 parts of a calcium-containing compound, 0.5-5 parts of polyacrylamide and 0.1-2 parts of inorganic base, wherein the binding agent is selected from one of glycerol, starch, methylcellulose, polypropylene glycol, alumina sol and sodium silicate; the magnesium-containing compound is selected from one of MgO, Mg(OH)2, Mg(CO3)2, Mg(OAc)2 and MgCl2; the calcium-containing compound is selected from one of CaO, Ca(OH)2, Ca(CO3)2 and CaCl2; the inorganic base is selected from one of NaOH, KOH, Na2CO3 and K2CO3. The catalyst is used for preparing guaifenesin, is simple and convenient to operate, environmentally friendly, low in energy consumption and high in yield.