Ordered colloidal particle films with double layers and dual members could be prepared by stepbystep spincoating method. Monolayer film of larger sized PS or SiO2 colloids was utilized as template to selfassemble second layer of SiO2 colloidal particles with smaller diameter. The size ratio γ of smaller and larger colloidal particles was 0.20—0.56 in the composite films. Larger （L） and smaller （S） dual member colloidal particles formed composite crystalline doublelayer films with multifarious arraymodes, whose structures could be expressed as LSx （here, L represents larger sized particles, S represents smaller colloidal particles, and x represents the stoichiometry of larger and smaller colloidal particles）, and x=1, 2, …, 13. The performance of composite colloidal films were influenced mainly by several factors, including spincoating velocity, spincoating time, viscosity of suspension medium, number density of colloidal suspension, and the wetting properties of substrates, etc.. On the prerequisite of complete wetting between colloidal suspension and substrate, appropriate number density of colloidal suspension, velocity and time of spincoating were the necessary conditions for ordered selfassembling to crystalline film of colloidal particles by spincoating method.