The cleaving of a novel microstructured polymer optical fiber (mPOF) to obtain an acceptable connectorized fiber end-face is studied. The effect of the blade temperature and the speed of the cutting blade on the end-face is qualitatively assessed. Recently manufactured mPOFs with air-structured 3- and 4-ring hexagonal-like hole cladding structures with outer fiber diameters of around 250 μm are employed. Good quality end-faces can be obtained by cleaving mPOF fibers at room temperature for blade temperatures within the range 60–80 °C and at a low blade speed at 0.5 mm/s. The importance of the blade surface quality is also addressed, being a critical condition for obtaining satisfactory mPOF end-faces after cleaving. From our experiments, up to four fiber cuts with the same razor blade and blade surface can be carried out with acceptable and similar fiber end-face results.