Recent advances in sample digestion and preconcentration used for rhenium and osmium isotope analysis in geological samples were reviewed. It summarized that the cation or anion exchange chromatography and solvent extraction technologies for separation and concentration of Re, and conventional distillation, micro-distillation, in situ distillation and solvent extraction technologies for separation and concentration of Os. It also summaried the experience of sample decomposition and preconcentration for Re and Os in geological samples.