The intrinsic flammability of polyamide 6 (PA6) has significantly impeded its broad application regardless of its balanced physical properties. Aluminum diethylphosphinate (ADP), as a P-containing fire retardant, has been demonstrated to be effective in reducing flammability of PA6 because of its dual-phase modes of action by creating an intact protective char layer and inhibiting the burning process. However, the efficiency of ADP needs to be further improved for creating cost-effective fire-retardant PA6, in addition to its relatively high cost. To boost its efficiency, we, here, report a P/N/B-containing aggregate (MBA) as an effective synergist via green self-assembly of melamine (MA), boric acid (BA) and amino trimethylene phosphonic acid (ATMP) in an aqueous medium. The results show that the inclusion of 5 wt% MBA and 10 wt% ADP leads to a significantly reduced peak heat release rate (PHRR) by 52.5% compared to neat PA6, in addition to a desired UL-94 V-0 rating. A synergistic effect of 55.4 % is observed between MBA and ADP in terms of the PHRR value. This work provides a facile green strategy for developing eco-friendly multiple elements-containing fire retardants, which can be used as fire retardants alone or high-efficiency synergists for other fire retardants.