Research has documented significant influences of parental psychological well-being on parenting. Yet, few studies have examined multiple measures of psychological well-being simultaneously to understand the underlying pathways and mediation factors. The present study employed new parents, without chronically high depressive symptoms, to examine across-time associations between the frequency of story reading and multiple measures of parental psychological well-being, namely the depressive symptoms, self-esteem, and global sense of personal control, in the first six years after becoming parents. Cross-lagged panel models with three time intervals were constructed to examine the across-time associations with 177 new parents. Significant direct and indirect effects between parental psychological well-being and story reading in the first six years after childbirth were identified. In the first three years after childbirth, new parents with more depressive symptoms and lower self-esteem tended to engage in more frequent story reading. New parents’ global sense of personal control, when the child was one to three years old, had a direct positive effect on story reading two to three years later. Through the mediation of self-esteem, parents with low psychological well-being after childbirth tended to engage in more frequent story reading when the child was three to six years old. Furthermore, the indirect effects of story reading on parental well-being were mediated by self-esteem and global sense of personal control. Findings from the present study underscored the importance of considering multiple measures of psychological well-being in understanding the bidirectional interactions between new parents’ well-being and early story reading in early family context.