AbstractPolyethylmethacrylate (PEM) was prepared by bulk polymerization and fractionated using acetone/acetone‐water (2:1 V/V) mixture. The solution properties of fractionated as well as unfractionated polymers were investigated in various solvents (ethylacetabte, toluene, ethylacetate‐ethanol) by light scattering and viscosity at 35°C. Osmotic pressure measurements were also carried out on selected polymer samples for the evaluation of width of distribution. [η]–Mwand (r2)1/2–Mwrelationships for these systems were established. Ethylacetate was found to be a bad solvent compared to toluene and methylethyketone. In the case of unfractionated PEM, the parameters like [η]2/3M1/3,Mw/[η], and Φ were corrected for molecular weight heterogeneity assuming SCHULZ‐ZIMM distribution. For the evaluation of FLORY's constant K, and the unperturbed dimension (r 20)1/2of the polymer, FLORY‐FOX, KURATA‐STOCKMAYER, and STOCKMAYER‐FIXMAN methods were employed. The K and (r 20)1/2values evaluated from the FLORY‐FOX method were almost similar to those measured in a Θ solvent, while the other two methods yielded higher values. A comparison of the measured (r2) 1/2wand that calculated from KIRKWOOD‐RISEMAN and DEBYE‐BUECHE theories indicated the polymer coil as conforming to a statistical chain. The molecular weight dependence of A2, the second virial coefficient, for PEM/ethylacetate was established and the value of A2compared well with that calcu