We report for the first time isolation of Ca@C92 and Ca@C94 by multi-stage highperformance liquid chromatography technique without recycling equipment. It is notable that higher metallofullerenes containing alkaline earth metal ions could be isolated although their relative yields are extremely low. Ca@C92 and Ca@C94 are also confirmed by LD-TOF mass spectrometry and characterrized by UV-Vis-NIR absorption measurements.
