Despite substantial technical advances and wider clinical use, cochlear implant (CI) users continue to report high and elevated listening effort especially under challenging noisy conditions. Among all the objective measures to quantify listening effort, pupillometry is one of the most widely used and robust physiological measures. Previous studies with normally hearing (NH) and hearing-impaired (HI) listeners have shown that the relation between speech performance in noise and listening effort (as measured by peak pupil dilation) is not linear and exhibits an inverted-U shape. However, it is unclear whether the same psychometric relation exists in CI users, and whether individual differences in auditory sensitivity and central cognitive capacity affect this relation. Therefore, we recruited 17 post-lingually deaf CI adults to perform speech-in-noise tasks from 0 to 20 dB SNR with a 4 dB step size. Simultaneously, their pupillary responses and self-reported subjective effort were recorded. To characterize top-down and bottom-up individual variabilities, a spectro-temporal modulation task and a set of cognitive abilities were measured. Clinical word recognition in quiet and Quality of Life (QoL) were also collected. Results showed that at a group level, an inverted-U shape psychometric curve between task difficulty (SNR) and peak pupil dilation (PPD) was not observed. Individual shape of the psychometric curve was significantly associated with some individual factors: CI users with higher clinical word and speech-in-noise recognition showed a quadratic decrease of PPD over increasing SNRs; CI users with better non-verbal intelligence and lower QoL showed smaller average PPD. To summarize, individual differences in CI users had a significant impact on the psychometric relation between pupillary response and task difficulty, hence affecting the interpretation of pupillary response as listening effort (or engagement) at different task difficulty levels. Future research and clinical applications should further characterize the possible effects of individual factors (such as motivation or engagement) in modulating CI users’ occurrence of ‘tipping point’ on their psychometric functions, and develop an individualized method for reliably quantifying listening effort using pupillometry.