Large language models (LLMs) exhibit uneven performance across languages. In language-specific applications, practitioners often rely on target-language corpora or cross-lingual transfer to achieve better performance. However, traditional linguistic typology, commonly used as a transfer language selection strategy in previous studies, may not align with LLM’s perception of language similarity. This work proposes LLM-based language similarity as a novel perspective for selecting effective fine-tuning languages. We construct a framework to quantify the similarity within each language pair through both the lenses of language-specific performance patterns and cross-lingual transferability, ultimately deriving three similarity score matrices. Moreover, we observe a counter-intuitive phenomenon: super-additive transfer effect, where fine-tuning on a certain language yields higher performance than fine-tuning directly on the target language. Additionally, due to the absence of an existing dataset meeting our experimental requirements, we construct and release M4CQ-Pro dataset, which features domain-diverse distribution of 135 tasks and content consistency across 31 languages (including over 20 medium- and low-resource languages), with 61518 manually reviewed high-quality questions per language. We evaluate our approach on representative multilingual LLMs and results show that all three LLM-based similarity measures effectively guide fine-tuning language selection, outperforming traditional linguistic similarity, with the integrated measure achieving the best results. Our approach provides not only a novel perspective on language similarity, but also practical baselines for selecting fine-tuning languages.