This study examined the processing and acquisition of novel words and their collocates (i.e., words that frequently co-occur with other words) from reading and the effect of frequency of exposure on this process. First and second language speakers of English read a story with 1) eight exposures of adjective-pseudoword collocations, 2) four exposures of the same collocations, or 3) eight exposures of control collocations. Results of recall and recognition tests showed that participants acquired knowledge not only of the form and meaning of the pseudowords but also of their collocates. The analysis of eye movements showed a significant effect of exposure on the processing of novel collocations for both first and second language readers, with reading times decreasing as a function of exposure. Eight exposures to novel adjective-pseudoword collocations were enough to develop processing speed comparable to that of known collocations. However, when analyzing the processing of the individual components of the collocations, results showed that eight exposures to the pseudowords were not enough for second language readers to develop processing speed comparable to known words. The frequency manipulation in the present study (four vs. eight exposures) did not lead to differences in the learning or processing of collocations. Finally, reading times were not a significant predictor of vocabulary gains.