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Ceramic wasteforms designed to be processed by melting in air has been developed to immobilise Cs-rich wastes. Detailed characterisation electron microscopy is presented on versions of these melted materials which are rich in Cr-, Ni-, Zn or Co- substituted titanate hollandites and which have PCT-B normalised Cs leachate concentrations of < 0.2 g/L. To assist in understanding the general crystal chemistry of titanate hollandites, this study also investigates the solubility limits of Cs in single-phase hollandite BaxCsy(M3+)2x+yTi8–2x-yO16 where M = Cr and BaxCsy(M2+)x+y/2Ti8-x-y/2O16 formulations where M = Zn, Co or Ni.