The invention discloses a honeycomb de-nitration catalyst suitable for high-arsenic fume and a preparation method of the honeycomb de-nitration catalyst. The catalyst is a V2O5-MoO3-TiO2 system catalyst, and the catalyst comprises the following components in parts by weight: 77-96 parts of TiO2, 1.5-10 parts of MoO3, 0.15-3 parts of V2O5, and 2-10 parts of SiO2. The invention discloses a preparation method of the catalyst. According to the honeycomb de-nitration catalyst disclosed by the invention, molybdenum is added to a conventional V-Ti system catalyst, an organic additive is changed, and an inorganic additive is added, so that a hole structure is enriched, and the arsenic poisoning resistance of the de-nitration catalyst is improved. The molybdenum can react with vanadium in the catalyst to generate a metal complex, so that the vanadium can be protected, and the vanadium is prevented from generating vanadium arsenate and poisoning deactivation; and the rich hole structure of the catalyst enables the catalytic reaction to have an enough place, and besides, the speed that As2O3 blocks ducts can be decelerated.