The hypothalamic neuropeptides arginine vasopressin (AVP) and oxytocin (OT) modulate social behavior across a wide variety of species. However, the role of arginine vasotocin (AVT) and isotocin (IT, the teleost homologs of AVP and OT) in regulating biparental care especially in the context of monogamy is not well studied. Here, using high-performance liquid chromatography (HPLC), we investigated how bioactive whole brain AVT and IT neuropeptide levels vary in relation to the phase of the breeding cycle and sex, in a monogamous biparental cichlid fish, Neolamprologus caudopunctatus. Since non-caring individuals of this species readily cannibalize eggs, but caring parents never do, we further investigated whether there might be changes in AVT/IT whole brain levels that correspond to the transition from a non-breeding, egg cannibal to an egg caring parent. We found that AVT levels were higher in females than in males and that AVT levels were highest when the need to defend the young was greatest. Breeding pairs that had a strong pair-bond and a higher frequency of nest care had the highest levels of AVT, whereas individuals that spent little time close to their breeding partner, displayed aggression towards their partner and neglected their nest duties (signs of a weak pair bond), had lower whole brain AVT levels. Isotocin (IT) levels did not differ between sexes and we did not detect any variation across the breeding cycle, with pair-bonding scores or with parental behavior. Our results show that whole brain AVT levels are linked to the breeding cycle, nest maintenance and pair-bonding score in this species. Furthermore, our study highlights species and sex-specific nonapeptides patterns in bi-parental caring fish and contributes to the increasing knowledge on neuroendocrinological mechanisms underlying parental care.