Microwave-accelerated ring-opening polymerization (ROP) of cyclic esters catalyzed by ionic liquid (IL) anions, intercalated into layered double hydroxides (LDHs), has been recently described as a fast and environmentally friendly synthetic way to prepare biodegradable polyester/LDH nanocomposites. However, to observe this synergistic catalytic effect between microwaves and IL anions and to achieve a homogeneous structure of the final polymer nanocomposite, the IL anions must be efficiently intercalated inside the LDH structure. Herein, we investigate the effects of various metal compositions of M2+/Al3+ LDHs (M = Mg, Co, and Ca) and different LDH synthetic routes (one-step direct coprecipitation, two-step coprecipitation/anion exchange, and two-step urea/anion exchange) on the intercalation efficiency of trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate IL. The most effective IL anion intercalation was observed for Ca2+/Al3+ LDH prepared using the two-step method consisting of coprecipitation and subsequent anion exchange. After optimization, this synthetic pathway led to the production of LDHs with intercalated IL anions and a reduced amount of intercalated water (<0.6 wt %). The catalytic ability of thus optimized LDH particles was demonstrated on the microwave-assisted ROP of ε-caprolactone, showing rapid progress of polymerization. Within minutes, the polycaprolactones with an average molecular mass in the range of 20 000-50 000 g/mol containing fully delaminated and exfoliated LDH nanoparticles were obtained.