Directed self-assembly of block copolymers is a promising candidate to address grand challenges towards new generations of low-cost, high-resolution nanopatterning technology. Over the past decade, poly(styrene-b-methyl methacrylate) (PS-b-PMMA) has been the most popular block copolymer applied in this area. However, further scaling towards pitches below 20 nm is hindered by its relatively low segregation strength between constituent blocks, characterized by a low Flory-Huggins interaction parameter, χ (~ 0.038 at r.t). To reach sub-10 nm feature dimensions, many high- χ block copolymer materials and processes are currently being studied. Here we investigate the DSA of PSb- PMMA with blended ionic liquid (IL) on chemically-patterned substrates via thermal annealing with a free surface. In this materials system, by adding low volume fraction of IL, a substantially higher χ than the pure block copolymer is achieved with manageable change in surface and interfacial properties so that poly(styrene-random-methyl methacrylate) brushes may be used to control substrate wetting behavior, and the blend could be assembled using thermal annealing with a free surface. In other words, PS-b-PMMA/IL may serve as a high- χ drop-in replacement for PS-b-PMMA. In this work, we provide key DSA results to determine if PS-b-PMMA/IL blends would offer a solution for sub-10 nm lithography.