Healthy aging is often associated with speech comprehension difficulties in everyday life situations despite a pure-tone hearing threshold in the normative range. Drawing on this background, we used a multidimensional approach to assess the functional and structural neural correlates underlying age-related temporal speech processing while controlling for pure-tone hearing acuity. Accordingly, we combined structural magnetic resonance imaging and electroencephalography, and collected behavioral data while younger and older adults completed a phonetic categorization and discrimination task with consonant-vowel syllables varying along a voice-onset time continuum. The behavioral results confirmed age-related temporal speech processing singularities which were reflected in a shift of the boundary of the psychometric categorization function, with older adults perceiving more syllable characterized by a short voice-onset time as /ta/ compared to younger adults. Furthermore, despite the absence of any between-group differences in phonetic discrimination abilities, older adults demonstrated longer N100/P200 latencies as well as increased P200 amplitudes while processing the consonant-vowel syllables varying in voice-onset time. Finally, older adults also exhibited a divergent anatomical gray matter infrastructure in bilateral auditory-related and frontal brain regions, as manifested in reduced cortical thickness and surface area. Notably, in the younger adults but not in the older adult cohort, cortical surface area in these two gross anatomical clusters correlated with the categorization of consonant-vowel syllables characterized by a short voice-onset time, suggesting the existence of a critical gray matter threshold that is crucial for consistent mapping of phonetic categories varying along the temporal dimension. Taken together, our results highlight the multifaceted dimensions of age-related temporal speech processing characteristics, and pave the way toward a better understanding of the relationships between hearing, speech and the brain in older age.