An underlying mechanism is reported for the formation of highly uniform crystalline organic semiconductor films by the double-shot inkjet printing (IJP) technique utilizing antisolvent crystallization. It is demonstrated that the ability to form uniform films with this technique can be attributed to the unique nature of the initial contact dynamics between the chemically different microdroplets before occurrence of solute crystallization. Experiments are conducted systematically where a single microdroplet is over-deposited by the IJP technique on a chemically different sessile droplet, for ten kinds of pure and miscible solvent combinations. The subsequent behavior is observed by high speed camera. The initial contact dynamics can be classified into three dramatically different cases that are respectively referred to as wetting, dewetting, and sinking. These phenomena are unique to microdroplets and the conditions for the occurrence of each type of phenomenon can be consistently explained by the fact that the initial contact dynamics are driven by the difference of surface tension of the liquids. Among the three kinds of dynamics, the wetting phenomenon creates a thin solution layer on the antisolvent droplet surface and can be used thus to manufacture uniform semiconductor films, where the coffee ring effect can be eliminated.