A perfect isotactic poly(methacrylic acid) (it‐PMAA) is synthesized and characterized by NMR spectroscopy. Surface pressure versus mean area per repeat unit (π−A) isotherms are recorded and compared with atactic poly(methacrylic acid) (at‐PMAA). it‐PMAA exhibits a π−A isotherm, indicating the formation of a stable Langmuir film. The isotherm has a characteristic pseudo‐plateau at π of ≈11–14 mN m−1 attributed to the creation of worm‐like entities confirmed by atomic force microscopy (AFM) in Langmuir–Blodgett (LB) films. These structures transform into spherical nanoparticles of ≈40 to 80 nm seen in LB films transferred at the end of the pseudo‐plateau of the isotherm. Grazing incidence wide‐angle X‐ray scattering (GI‐WAXS) shows a broad scattering signal (halo‐like) at a q position of ≈11.12 nm−1, revealing the amorphous nature of the nanoparticles. An ordered morphology, however, is observed in thin films prepared by precipitating it‐PMAA from dimethylformamide (DMF) solution under vigorous stirring and coating them on a solid support. Optical microscopy (OM), AFM, and GI‐WAXS reveal more details about the structure. Finally, various structural modifications of PMAAs are explained based on their tacticity and the subsequent hydrogen bonding effects between the carboxylic acid groups.