The content and composition of pigments and CIELab color properties in fruits ripened in the field were compared with those obtained in ground paprika produced from green pepper fruits after postharvest ripening for 15 days in a greenhouse under different conditions. Obtained data for pigment content, composition, and esterification rate have shown that the processes of pigment biosynthesis in fruits ripened under greenhouse conditions are different from those occurring in fruits naturally matured in the field: the red/yellow pigment ratio (3:1) in greenhouse-ripened fruits is much higher than in naturally ripened pepper in breaker (1:1) and also in faint red (2:1) ripening stages from the field. Additionally, during the postharvest ripening of green pepper in the greenhouse esterification processes are less expressed than during the ripening of the fruits in the field. Postharvest ripening under natural daylight resulted in higher content of red pigments, followed by higher ASTA value.