The coalescence between growing droplets is important for the surface coverage and spatial arrangements of droplets on surfaces. In this work, total internal reflection fluorescence (TIRF) microscopy is utilized to in situ investigate the formation of nanodroplets around the rim of a polymer microcap, with sub-micron spatial and millisecond temporal resolution. We observe that the coalescence among droplets occurs frequently during their growth by solvent exchange. Our experimental results show that the position of the droplet from two merged droplets is related to the size of the parent droplets. The position of the coalesced droplet and the ratio of parent droplet sizes obey a scaling law, reflecting a coalescence preference based on the size inequality. As a result of droplet coalescence, the angles between the centroids of two neighbouring droplets increase with time, obeying a nearly symmetrical arrangement of droplets at various time intervals. The evolution of the position and number from coalescence of growing droplets is modelled. The mechanism for coalescence driven self-organization of growing droplets is general, applicable to microcaps of different sizes and droplets of different liquids. The understanding from this work may be valuable for positioning nanodroplets by nucleation and growth without using templates.