An alpha, omega-dihydroxypoly(fluorooxetane) was prepared from a fluorinated oxetane monomer and characterized by matrix-assisted laser desorption ionization mass spectrometric (MALDI MS) and gel permeation chromatographic (GPC) methods. Estimated molecular weights were compared to those derived from NMR spectroscopic end-group analysis. The results of 2-D NMR spectroscopic analysis agreed well with 1-D NMR end-group analytical results and MALDI MS experiments. Because of the small molecular weight of the product, the results from the mass spectroscopic and NMR methods compared favorably. The overestimated molecular weights obtained from GPC are explained by aggregation of the amphiphilic poly(fluorooxetane) in a relatively poor solvent. The robustness of the methods was verified by fractionation of the polymer and subsequent analysis of the fractions by MALDI MS. In addition, information regarding product architecture and copolymerization with THF, which was used to complex the BF3 catalyst, was obtained using tandem mass spectrometry (MS/MS) methods.