Conventional mapping of a phase diagram of a polymer in a solvent requires a substantial amount of polymer (e.g., at least of the order of,similar to 100 mg of narrowly distributed samples with different molar masses) and may take months or even years to reach the true two phase equilibrium at each given temperature, especially when the polymer concentration is high. This is why good phase diagrams of polymer solutions are rare in the literature. To solve such a problem, we developed a Teflon microfluidic device to prepare and store a series of droplets (similar to 10 nL) at different polymer concentrations inside a glass capillary. The phase transition inside each polymer solution droplet sealed and isolated in immiscible fluorohydrocarbon could be quickly and precisely monitored by a newly developed small angle laser light scattering detector. Using poly(vinyl acetate) (PVAc) in isobutyl alcohol and in benzene as two examples, we demonstrated that a combination of microfluidic device and small angle light scattering enables us to map the phase diagram of a polymer in a given solvent within hours by using only a few mg of the sample because (1) each droplet contains no more than similar to 10 mu g polymer and (2) the phase-transition induced interchain association inside each droplet can be quickly and sensitively detected. We have demonstrated that two sets of a total of eight precisely mapped phase diagrams of four PVAc fractions in the two solvents can be reasonably scaled together to form a master curve.