The choice of token vocabulary affects the performance of machine translation. This paper aims to figure out what is a good vocabulary and whether we can find the optimal vocabulary without trial training. To answer these questions, we first provide an alternative understanding of vocabulary from the perspective of information theory. It motivates us to formulate the quest of vocabularization – finding the best token dictionary with a proper size – as an optimal transport (OT) problem. We propose VOLT, a simple and efficient solution without trial training. Empirical results show that VOLT beats widely-used vocabularies in diverse scenarios, including WMT-14 English-German translation, TED bilingual translation, and TED multilingual translation. For example, VOLT achieves 70% vocabulary size reduction and 0.5 BLEU gain on English-German translation. Also, compared to BPE-search, VOLT reduces the search time from 384 GPU hours to 30 GPU hours on English-German translation. Codes are available at https://github.com/Jingjing-NLP/VOLT.