Episodic memory (EM) is particularly sensitive to pathological conditions and aging. In a neurocognitive context, the paired-associate learning (PAL) paradigm, which requires participants to learn and recall associations between stimuli, has been used to measure EM. The present study aimed to explore whether functional near-infrared spectroscopy (fNIRS) can be employed to determine cortical activity underlying encoding and retrieval. Moreover, we examined whether and how different aspects of task (i.e., novelty, difficulty) affects those cortical activities. Twenty-two male college students (age: M = 20.55, SD = 1.62) underwent a face-name PAL paradigm under 40-channel fNIRS covering fronto-parietal and middle occipital regions. A decreased activity during encoding in a broad network encompassing the bilateral frontal cortex (Brodmann areas 9, 11, 45, and 46) was observed during the encoding, while an increased activity in the left orbitofrontal cortex (Brodmann area 11) was observed during the retrieval. Increased HbO concentration in the superior parietal cortices and decreased HbO concentration in the inferior parietal cortices were observed during encoding while dominant activation of left PFC was found during retrieval only. Higher task difficulty was associated with greater neural activity in the bilateral prefrontal cortex and higher task novelty was associated with greater activation in occipital regions. Combining the PAL paradigm with fNIRS provided the means to differentiate neural activity characterising encoding and retrieval. Therefore, the fNIRS may have the potential to complete EM assessments in clinical settings.