The preparation and characterization of poly(ionic liquid)s (PILs) bearing a polystyrene backbone via reversible addition fragmentation chain transfer (RAFT) polymerization and their photolithographic patterning on silicon wafers is reported. The controlled radical polymerization of the styrenic ionic liquid (IL) monomers ([BVBIM]X, X = Cl- or Tf2N-) by RAFT polymerization is investigated in detail. We provide a general synthetic tool to access this class of PILs with controlled molecular weight and relatively narrow molecular weight distribution (2000 g mol-1 ≤ Mn ≤ 10-000 g mol-1 with dispersities between 1.4 and 1.3 for p([BVBIM]Cl); 2100 g mol-1 ≤ MP ≤ 14-000 g mol-1 for p([BVBIM]Tf2N)). More importantly, we provide an in-depth characterization of the PILs and demonstrate a detailed mass spectrometric analysis via matrix-assisted laser desorption ionization (MALDI) as well as-for the first time for PILs-electrospray ionization mass spectrometry (ESI-MS). Importantly, p([BVBIM]Cl) and p([DMVBIM]Tf2N) were photochemically patterned on silicon wafers. Therefore, a RAFT agent carrying a photoactive group based on ortho-quinodimethan ... mehre chemistry-more precisely photoenol chemistry-was photochemically linked for subsequent controlled radical polymerization of [BVBIM]Cl and [DMVBIM]Tf2N. The successful spatially-resolved photografting is evidenced by surface-sensitive characterization methods such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The presented method allows for the functionalization of diverse surfaces with poly(ionic liquid)s. © The Royal Society of Chemistry 2016.