Elastic electron scattering from gaseous methylformamide (N-methylformamide, C2H5NO) has been investigated. Absolute elastic differential cross sections (DCSs) were determined both experimentally and theoretically for the incident energies from 50 to 300 eV. The measurements were performed using a cross-beam technique, for scattering angles from 20◦ to 110◦. Relative elastic DCSs were measured as a function of both the angle and the incident energy and the absolute DCSs were determined using the relative flow method. The calculations of electron interaction cross sections are based on a corrected form of the independent-atom method, known as the SCAR (screen corrected additivity rule) procedure and using an improved quasifree absorption model. Calculated integral cross sections have been presented, as well, both for methylformamide and formamide, in the energy range 10–1000 eV, and discussed. The results are compared with and discussed regarding existing data for other small molecules representing building blocks of large biomolecules.