A hydrophilic inorganic porous catalyst was prepared via the hydrothermal method. The combination of [WZn3(H2O)2(ZnW9O34)2]12- and Co(ii) provides a synergistical catalytic way to promote oximation of aldehyde/ketone with in situ generated hydroxylamine that initially produces an oxime, which further either dehydrates into a nitrile or undergoes a Beckmann rearrangement to form an amide.