This study was aimed at evaluating the associations between maternal parenting practices (positive, negative/inconsistent, and punitive), children’s difficulties (such as conduct problems, emotional symptoms, peer problems, and hyperactivity), and prosocial behaviors. Participants were 131 Italian mothers of primary school children; mothers were aged between 26 and 52 years (M = 38.38, SD = 5.46); children (54% girls) were aged between 6 and 10 years (M = 7.15, SD = 0.98). Mothers completed two scales assessing their parenting practices and their children’s psychosocial adjustment. A path analysis was run to test the hypothesized model. The results showed the following: (a) maternal positive parenting was negatively and significantly related to children’s conduct problems and hyperactivity, and positively and significantly to children’s prosocial behavior; (b) maternal negative/inconsistent parenting was positively and significantly related to children’s conduct problems, emotional symptoms, and hyperactivity; (c) maternal punitive parenting was positively and significantly related to children’s conduct problems and emotional symptoms. Moreover, the results showed that, according to the mothers’ perceptions, boys tended to exhibit higher levels of hyperactivity and peer problems and lower levels of prosocial behaviors than girls. Overall, this study highlights the unique role of different maternal parenting practices in the psychosocial adjustment of primary school children.