The invention relates to a perovskite composite oxide catalyst for preparing methyl alcohol from methane as well as a preparation method of the catalyst, wherein the perovskite composite oxide catalyst for preparing the methyl alcohol from the methane is a particulate matter, and has the general formula of Me(x)O(y)-A(l-m)A'(m)B(1-n)B'(n)O(3), wherein m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, A is one of Ca and La, A' is one of Ba and Sr, B is one of Fe, Co, Ni and Mn, B' is one of Zr, Ti and Cr, and transition metal oxide Me(x)O(y) is one or two of Fe(2)O(3), N(i)O and Fe(3)O(4). The method provided by the invention is simple to operate, short in consumed time, and lower in operation expense by being compared with the operation expense in a traditional method for preparing the methyl alcohol from the methane. The catalyst provided by the invention can be used for oxidizing crystal lattices to prepare the methyl alcohol by CH4 at 500-500 DEG C; the methane conversion rate is 40-80%, and the methyl alcohol yield rate is 20-40%, and a novel method for preparing the methyl alcohol from the methane is provided.