This study investigates the linguistic understanding of Large Language Models (LLMs) regarding signifier (form) and signified (meaning) by distinguishing two LLM evaluation paradigms: psycholinguistic and neurolinguistic. Traditional psycholinguistic evaluations often reflect statistical biases that may misrepresent LLMs' true linguistic capabilities. We introduce a neurolinguistic approach, utilizing a novel method that combines minimal pair and diagnostic probing to analyze activation patterns across model layers. This method allows for a detailed examination of how LLMs represent form and meaning, and whether these representations are consistent across languages. Our contributions are three-fold: (1) We compare neurolinguistic and psycholinguistic methods, revealing distinct patterns in LLM assessment; (2) We demonstrate that LLMs exhibit higher competence in form compared to meaning, with the latter largely correlated to the former; (3) We present new conceptual minimal pair datasets for Chinese (COMPS-ZH) and German (COMPS-DE), complementing existing English datasets.