Speciation of fission products (90Sr,99Tc,137Cs and152Eu) in raw cow milk was studied using the high-performance size exclusion radiochromatography (HP-SERC) by Biosep-SEC-S® column (Phenomenex, USA). The separation fraction were identified by a UV detector (280 nm) and a scintillation radiodetector. The mobile phase was Jenness-Koops buffer that simulated milk serum. Radiocesium was present only in non-protein fractions. The non-protein fractions complexed 17% of technetium and 57% of strontium. About 32% of strontium and 24% of europium were bound on the high molecular weight proteins (micellar casein). Low molecular weight proteins bound about 11% of strontium and 76% of europium. Non-size effects play a dominant role at HPSERC speciation of technetium, 83% of which follow the lightest fractions of milk.