The role of the spatial structure of a turbulent flow in enhancing particle collision rates in suspensions is an open question. We show and quantify, as a function of particle inertia, the correlation between the multiscale structures of turbulence and particle collisions: Straining zones contribute predominantly to rapid head-on collisions compared to vortical regions. We also discover the importance of vortex-strain worm-rolls, which goes beyond ideas of preferential concentration and may explain the rapid growth of aggregates in natural processes, such as the initiation of rain in warm clouds.