Quality breakdown caused by high respiration, evaporation, and pigment degradation affects the storage ability and shelf life of pear fruit. Phenylalanine is an aromatic amino acid that can enhance the nutritional quality and disease resistance of vegetables and fruit. This study was conducted to assess the effects of exogenous phenylalanine on quality indicators, tricarboxylic acid (TCA) cycle, and chlorophyll catabolism of ‘Jinfeng’ pear fruit. Results showed that phenylalanine treatment declined a* value, b* value, ΔE, and malondialdehyde content, enhanced L* value, soluble solids and ascorbic acid contents, and titratable acidity, but delayed the decrease of flesh firmness. Phenylalanine also reduced pyruvate dehydrogenase, isocitrate dehydrogenase, aconitase, citrate synthase, fumarase, succinate dehydrogenase, and malate dehydrogenase activities and gene expressions as well as PcNADP-ME expression and α-keto glutaric dehydrogenase (α-KGDH) activity in the TCA cycle of pears. Moreover, phenylalanine suppressed the expression levels of PcNCY1, PcHCAR, PcCHL1, PcPAO, PcRCCR, PcPPH, and PcSGR1/2 in chlorophyll degradation. Meanwhile, phenylalanine treatment enhanced malic acid, citric acid, succinic acid, total chlorophyll, chlorophyll a, and chlorophyll b contents in pears. These results indicate that exogenous phenylalanine could keep the quality of pears after harvest by inhibiting the key gene expression and enzyme activity in the TCA cycle and chlorophyll degradation. These findings also suggest that phenylalanine can be used as a potential inducer to delay yellowing and maintain the postharvest quality of fruit.