The metabolism of carbohydrates, organic acids, amino acids and phenolics was compared between the sun-exposed peel and the shaded peel of apple fruit. Contents of sorbitol and glucose were higher in the sun-exposed peel, whereas those of sucrose and fructose were almost the same in the two peel types. This was related to lower sorbitol dehydrogenase activity and higher activities of sorbitol oxidase, neutral invertase and acid invertase in the sun-exposed peel. The lower starch content in the sun-exposed peel was related to lower sucrose synthase activity early in fruit development. Dark respiratory metabolism in the sun-exposed peel was enhanced by the high peel temperature due to high light exposure. Activities of most enzymes in respiratory metabolism were higher in the sun-exposed peel, but the concentrations of most organic acids were relatively stable, except pyruvate and oxaloacetate. Due to the different availability of carbon skeletons from dark respiration in the two peel types, amino acids with higher C/N ratios are accumulated in the sun-exposed peel whereas those with lower C/N ratios are accumulated in the shaded peel. Contents of anthocyanins and flavonols and activities of phenylalanine ammonia-lyase, UDP-galactose:flavonoid 3-O-glucosyltransferase and several other enzymes were higher in the sun-exposed peel than in the shaded peel, indicating the entire phenylpropanoid pathway is upregulated in the sun-exposed peel. Comprehensive analyses of the metabolites and activities of enzymes involved in primary metabolism and secondary metabolism have allowed us to gain a full picture of the metabolic network in the two peel types under natural light exposure.