The knowledge of the plastic type, thickness, and the nature of the surface is important towards the monitoring of microplastic pollution in water bodies, especially when vis-NIR spectroscopy is utilized. Factors such as complex environment and surface roughness induced-light scattering of the probing light limit the optical detection of these parameters in in-situ measurements, however. In this paper, a novel application of Kramers–Kronig analysis was exploited to identify both smooth and rough film-type macroplastics with unknown thickness. This method is particularly useful in the in-situ identification of unknown film-like macroplastics; although the sample is large, the ratio function is detected from an area that corresponds to the size of a MP. Therefore, it can be applied for the case of large size MPs. The validity of the method was demonstrated using transmittance data for smooth and roughened plastics given in Kanyathare et al., 2020.