We demonstrate a facile single step laser treatment process to render a polydimethylsiloxane (PDMS) surface superhydrophobic. By synchronizing a pulsed nanosecond laser source with a motorized stage, superhydrophobic grid patterns were written on the surface of PDMS. Hierarchical micro and nanostructures were formed in the irradiated areas while non-irradiated areas were covered by nanostructures due to deposition of ablated particles. Arrays of droplets form spontaneously on the laser-patterned PDMS with superhydrophobic grid pattern when the PDMS sample is simply immersed in and withdrawn from water due to different wetting properties of the irradiated and non-irradiated areas. The effects of withdrawal speed and pitch size of superhydrophobic grid on the size of formed droplets were investigated experimentally. The droplet size increases initially with increasing the withdrawal speed and then does not change significantly beyond certain points. Moreover, larger droplets are formed by increasing the pitch size of the superhydrophobic grid. The droplet arrays formed on the laser-patterned PDMS with wettability contrast can be used potentially for patterning of particles, chemicals, and bio-molecules and also for cell screening applications.