The aim of this research was to study the relationships between electronic nose (E-nose) pattern, maturity class of peaches assessed at harvest by means of absorption coefficient at 670 nm (μ(a)670) measured in fruit pulp by time-resolved reflectance spectroscopy (TRS), and quality evolution during a 4 week cold storage. 'Spring Belle' peaches were measured for μ(a)670 by TRS, ranked according to decreasing μ(a)670 value, divided into three TRS maturity classes (less (LeM), medium (MeM), and more (MoM) mature), and randomized into 9 samples of 30 fruit each, so that fruits from the whole μ(a)670 range were present in each sample. At harvest and after 1, 2, 3, and 4 weeks of storage at 0 and 4 °C, fruits of each sample were evaluated for firmness, expressible juice, μ(a)670, and ethylene production. LeM and MoM peaches of each sample were analyzed for aroma pattern by a commercial electronic nose and by static HS-GC and for sugar (glucose, fructose, sucrose, and sorbitol) and organic acid (quinic, malic, and citric acids) compositions by HPLC. Principal component analysis (PCA) of electronic nose data emphasized the ability of the E-nose to assess the ripening stage of fruit associated with maturity class, storage time, and storage temperature. The sensors having the highest influence on the pattern were W5S in PC-1, W1S in PC-2, and W2S in PC-3. From linear correlation analysis between PCs and firmness, flavor, and volatile compounds, it was found that PC-1 was related to ethylene production and volatile compounds (mainly acetate esters and ethanol); the highest PC-1 scores were found for fruit belonging to the MoM class after 2 weeks of storage at 4 °C, which showed the rise in ethylene production coupled with the highest total volatile production and sugar and acid composition of ripe peach fruits. PC-2 correlated with hexanal, ethyl acetate, and sugar composition, and PC-3 was mainly related to flavor compounds; both functions significantly changed with cold storage time in different ways according to storage temperature and maturity class.