Very large numbers words such as “hundred,” “thousand,” “million,” “billion,” and “trillion” pose a learning problem for children because they are sparse in everyday speech and children's experience with extremely large quantities is scarce. In this study, we examine when children acquire the relative ordering of very large number words as a first step toward understanding their acquisition. In Study 1, a hundred and twenty-five 5–8-year-olds participated in a verbal number comparison task involving very large number words. We found that children can judge which of two very large numbers is more as early as age 6, prior to entering first grade. In Study 2, we provided a descriptive analysis on the usage of very large number words using the CHILDES database. We found that the relative frequency of large number words does not change across the years, with “hundred” uttered more frequently than others by an order of magnitude. We also found that adults were more likely to use large number words to reference units of quantification for money, weight, and time, than for discrete, physical entities. Together, these results show that children construct a numerical scale for large number words prior to learning their precise cardinal meanings, and highlight how frequency and context may support their acquisition. Our results have pedagogical implications and highlight a need to investigate how children acquire meanings for number words that reference quantities beyond our everyday experience.