Poly(4-vinyl phenol)(PVPh) was neutralized by LiOH and PVPh ionomers(PVPh-Li) with different Li neutralization extents were synthesized. The variation in T_g with Li neutralization was determined by DSC and the results show that the T_gincreases by 3.8 ℃ per Li mol%. When comparing this result with the 3.2 ℃ per Na mol% reported for poly(styrene-co-hydroxy styrene), the greater value for PVPh-Li may be due to a strong interaction between unneutralized free -OH and -OLi produced. No distinct small angle X-ray scattering(SAXS) peak was observed for these PVPh ionomers in bulk. In the 50/50 blend of PVPh-Li with PVPh, the miscibile blend was obtained when the Li neutralization in PVPh-Li was 10 mol%. On the contrary, the 50/50 PVPh-Li/PMMA was immiscible when the Li neutralization was 5 mol%. It can be concluded that, even if the staring blend is miscible owing to hydrogen bonding, the miscibility of blend becomes diminished by introducing small amount of ion groups into one of the constituent polymers and the blend can be immiscible as long as any new strong intermolecular ion-dipole interaction is not generated.