Provided are methods for obtaining modified polyarylene sulfide compositions having improved thermal and thermo-oxidative stability, the compositions so obtained, and articles comprising the compositions. The method comprises the steps of contacting, in the presence of a suitable solvent, a polyarylene sulfide with at least one reducing agent and at least base to form a first mixture. The reducing agent comprises zinc(0), tin(0), tin(II), bismuth (0), bismuth(III), or a combination thereof. The first mixture is heated to form a second mixture in which the polyarylene sulfide is dissolved. The polyarylene sulfide is then precipitated to obtain a modified polyarylene sulfide.