The reaction of [µ₄-Ge{Co₂(CO)₇}₂] with [Co(CO)₄]⁻ has been monitored by electrospray mass spectrometry to detect the cluster anions generated. Conditions giving known mixed Ge–Co carbonyl clusters were established, and a new high nuclearity cluster anion, [Ge₂Co₁₀(CO)₂₄]²⁻ was detected. Conditions for its formation were optimised and it was subsequently isolated as its [Et₄N]⁺ salt and characterised by single-crystal X-ray crystallography. The Ge₂Co₁₀ cluster core has a novel geometry with the two germanium atoms in semi-encapsulated positions, forming seven formal Ge–Co bonds. There are also eighteen formal Co–Co bonds. Corresponding reactions of [µ₄-Si{Co₂(CO)₇}₂] with [Co(CO)₄]⁻ were also investigated.