Particle-laden droplet-based systems ranging from micro- to nanoscale have become increasingly popular in applications such as inkjet printing, pharmaceutics, nanoelectronics, and surface patterning. All such applications involve multidroplet arrays in which vapor-mediated interactions can significantly affect the evaporation dynamics and morphological topology of precipitates. A fundamental study was conducted on nanocolloidal paired droplets (droplets kept adjacent to each other as in an array) to understand the physics related to the evaporation dynamics, internal flow pattern, particle transport, and nanoparticle self-assembly, primarily using optical diagnostic techniques [such as micro-particle image velocimetry (μPIV)]. Paired droplets exhibit contact angle asymmetry, inhomogeneous contact line slip, and unique single-toroid microscale flow, which are unobserved in single droplets. Furthermore, nanoparticles self-assemble (at the nanoscale) to form a unique variable-thickness (microscale) tilted dome-shaped structure that eventually ruptures at an angle because of evaporation at a nanopore scale to form cavities (miniscale). The geometry and morphology of the dome can be further fine-tuned at a macro- to microscale by varying the initial particle concentration and substrate properties. This concept has been extended to a linear array of droplets to showcase how to custom design two-dimensional drop arrangements to create controlled surface patterns at multiple length scales. © 2016 American Chemical Society.