The invention provides a preparing method of a carbon nano tube array composite film and a heat exchanger. The method comprises the following steps that S1, an Al2O3 film and a Fe film are sequentially deposited on a substrate of monocrystalline silicon (100) to serve as catalysts; S2, vacuum chemical vapor deposition equipment is heated to 830 DEG C to 850 DEG C, ethylene gas is led in to serve as a carbon source, and a carbon nano tube array grows under assistance of water; S3, paracyclophane is deposited on the surface of the nano tube array in a vapor manner to form an even composite film; S4, the composite film is transferred to an aluminum sheet from the substrate of the monocrystalline silicon (100), paracyclophane is deposited on the surface of the composite film in a vapor manner, and a composite film is bonded on the aluminum sheet; and S5, a paracyclophane coating on the surface of the composite film is etched to form the carbon nano tube array composite film. The prepared carbon nano tube array composite film has high temperature and low temperature resistance, corrosion resistance, heat conduction and super hydrophobicity, and therefore when a unit carries out refrigeration, heat exchanger fins are not prone to condensation; and during heating, frosting is not prone to happening, the heat exchange performance of the heat exchanger is improved, and therefore the running performance of the unit is improved.