A free radical solution process for making PVP polymers having a molecular weight corresponding to a K-value of about 30-150, a narrow molecular weight distribution represented by a polydispersity of about 3 to 6, and a residual VP monomer level of less than 0.1%, which comprises:(a) precharging a reaction mixture of vinylpyrrolidone monomer and water in a solids contents w/w VP/H.sub.2 O of about 5-50%, and a dual free radical initiator system which comprises both low and high decomposition temperature free radical initiators whose 10-hour half-life temperature decomposition constants differ from each other by more than 5.degree. C., the low and high temperature initiators being present, respectively, in an amount of about 0.05-0.5%, and about 0.1-0.5%, by weight of the VP monomer,(b) polymerizing said monomer in said reaction mixture at a temperature near or above the 10-hour decomposition temperature of said low temperature initiator, and(c) after substantially all of the VP monomer has been converted to PVP polymer, continuing the polymerization at the same temperature as in (b), or at a higher temperature near or above the decomposition temperature of the high 10-hour temperature initiator, to complete the polymerization and to reduce the residual VP monomer level to less than 0.1%.