A new synthetic methodology has been developed for the synthesis of poly BAMO and poly BAMO-co-THF with controlled molecular weight and narrow molecular weight distribution. The synthesis of BCMO,the precursor of the BAMO monomer was accomplished using the reaction of Vilsmeir reagent with pentaerythritol. The BAMO monomer could be synthesized with an over all yield of 60% and polymerized using BF3·Et2O as the initiator and 1,4-butane diol as the co-initiator. Computational evaluation of the energy releasing properties of the poly BAMO derivatives was performed using Gaussian algorithm. The theoretically calculated values agreed very well with the experimentally determined ones.