A temperature control mica/VO2 functional pearlescent pigment was designed for the packaging industry. Firstly, a layer of VO2 nanorod film was coated on the surface of flake mica powder by hydrothermal method. Then, the surface of pure mica was modified by silane coupling agent KH-570 and sandwiched between inorganic powders to strengthen the combination. Secondly, the mica/VO2 composite pearlescent powder with gray-green pearlescent effect were successfully obtained by thermal annealing. The crystal structure of the VO2 coating and the chemical valence state of vanadium were verified by X-ray diffraction and X-ray photoelectron spectroscopy. Finally, powders were mixed with polyurethane resin to obtain a functional film. The infrared transmittance of film at 28 °C and 70 °C showed that the composite film with mica content of 3 g had greater temperature control properties, and the difference between high and low temperature transmittance was about 16%. Most importantly, the shiny decorative effect of pearlescent pigment can be still be maintained after being endowed with temperature control property. This work proposes the preparation of functional mica/VO2 composite with pearlescent effect and temperature control property.