Large diversity of tailor-made poly[(epsilon-caprolactam)-co-(epsilon-caprolactone)] P[(CLA)-co-(CLO)] and poly[(epsilon-caprolactam)-co-(delta-valerolactone)] P[(CLA)-co-(VLO)] copolymers have been obtained via activated anionic polymerization of epsilon-caprolactam (CLA) with sodium caprolactam (NaCL) as a basic initiator. In the present study several poly(epsilon-caprolactones) (PCLOs) and poly(delta-valerolactone) polyols were employed as effective bifunctional polymeric activators (PACs) and suitable comonomers of CLA. The obtained poly(esteramides) PEAS were isolated and their structure was confirmed by the H-1 NMR and FTIR spectroscopy. The influence of the molecular weight and type of the PACs, the CLA/PAC ratio and polymerization conditions on the conversion, intrinsic viscosity and polymerization kinetic was explored. The results demonstrated that the use of the PACs reduces the polymerization time to several minutes and polymerization process proceeds without induction period at low energy of activation and high yield of copolymers. Evaluation of the PACs activity and the activation energy confirmed that the PACs are highly active compounds efficient to CLA features modification.