Amorphous polysiloxane nano- and microstructures with different shapes can be synthesized from trifunctional organosilane precursors. In the present study, various polysiloxane nano- and microstructures have been produced via a chemical vapor deposition process using ethyltrichlorosilane as precursor. The structure formation and shape are the result of a delicate interplay between temperature, absolute amount of water, and relative humidity. The impact of these reaction parameters during a chemical vapor deposition process has been examined. Experiments have been performed to find a correlation between the reaction conditions and the final shape. Scanning electron microscopy data show that different structures like polysiloxane microrings, microrods, sprouts, nanofilaments, and mixtures of them can be synthesized depending on the reaction conditions. Furthermore, the in-depth comparison of the nanofilament diameters illustrates the dominating influence of relative humidity on structure formation. There is a general trend that at a higher value of relative humidity, structures with a larger diameter are formed independent from the temperature. Here, we clearly differentiate between relative humidity as major and absolute amount of water and temperature as minor important adjusting screws defining the thickness and shape of the resulting nano- and microstructures. Based on these observations, we proof the mechanism of the initial step of structure formation. It is shown that nano- and micro-sized water droplets formed on the substrate surface are likely to act as starting points for structure formation. All results described here strongly confirm the recently published droplet assisted growth and shaping mechanism.