Evaporation of water and ethanol/water droplets containing large polystyrene (PS) microparticles on polydimethylsiloxane (PDMS) surface was experimentally investigated. It is found that no matter with or without small addition of ethanol, a compact monolayer deposition is formed for lower microparticle concentration while mountain-like deposition for higher concentration. Since the more volatile compound (ethanol) evaporates more quickly than the less volatile compound (water), evaporation of ethanol/water mixture droplet exhibits different characteristics from pure water. When the concentration of microparticle is low, the contact radius of ethanol/water mixture droplet decreases throughout the whole process, while the contact angle increases at first to a maximum, then keeps almost constant, and finally decreases sharply. However, the evaporation of ethanol/water mixture droplet with higher concentration of microparticle behaviors more complex. The settling time of microparticles was estimated and its theoretical value agrees well with the experimental one. Moreover, a mechanism of self-pinning of microparticles was used to elucidate the deposition behavior of microparticles, indicating that as the contact line is depinning, the liquid film covering the outmost microparticle becomes thicker and thicker, and the microparticles have to move spontaneously with the depinning contact line under the action of capillary force.