This study aims to characterize the pectic oligosaccharides (POSs) generated from enzymatically hydrolyzed citrus peel pectin using a selected enzyme. Pectinex Ultra AFP was used to depolymerize citrus peel pectin into POSs. The POSs were analyzed using high-performance liquid chromatography (HPLC) and liquid chromatography coupled with a mass spectrometer (LC/MS) methodology to determine the composition of monosaccharides and the average molar mass distribution based on the retention time. The identified fractions were predominantly neutral sugars (rhamnose, glucose, and galactose) and acidic sugars (galacturonic acid), with corresponding mole percentages of 8.67%, 10.28%, 74.33%, and 6.72%, respectively. The degree of polymerization (DP) was in the range of DP3–DP8, containing three (trimers) to eight (octamers) monomeric units. The low DP indicates an advanced degree of enzymatic hydrolysis of pectin up to the level of pectic POSs.