The requirement for good parental lines of pepper (Capsicum annuum L.) with high phytochemicals, especially for capsinoids (CATs) and capsaicinoids (CAPs), is rapidly increasing, and plant breeders are encouraged to develop new pepper varieties. The objective of this study was to estimate the general combining ability (GCA) and specific combining ability (SCA) for the contents of CATs and CAPs in pepper in two different environments. The mean performances for fresh yield, dry yield and phytochemical contents in C. annuum L. were significantly affected by the environment. The effect of additive gene action was significant in determining the traits of CAT, Sum CATs, CAT yield and Sum CAPs. Conversely, non-additive gene action played a crucial role in the accumulation of DI-CAT in this population. The parental lines 203, 201, 101 and 202 were identified as the best parents for fruit yield, sum CAPs, sum CATs and CAT yield, respectively, based on their high positive GCA values and mean actual values. The SCA estimates for fruit yield, sum CAPs and sum CATs were positive and high for the hybrids 102/203, 101/201 and 102/202, indicating that they hold promise for use in commercial hybrids.