The roll coating method is of considerable significance in several industries, as it is applied practically in the production of paint, the manufacturing of PVC-coated cloth, and the plastic industry. The current study theoretically and computationally analyses the Powell–Eyring fluids with variable viscosity during the non-isothermal roll-over web phenomenon. Based on the lubrication approximation theory (LAT), the problem was formulated. The system of partial differential equations (PDEs) obtained from the mathematical modeling was further simplified to a set of ordinary differential equations (ODEs) using suitable transformations. A regular perturbation method was implemented to obtain the solution in terms of velocity, pressure gradient, pressure, and flow rate per unit width. This study also captures important engineering characteristics such as coating thickness, Nusselt number, shear stress, roll/sheet separating force, and roll-transmitted power to the fluid. Along with a comparison between the present work and published work, both graphical and tabular representations wer made to study the effects of various factors. It was observed that the velocity profile is the decreasing function of non-Newtonian and Reynold viscosity parameters. In addition, the response surface methodology (RSM) was employed to investigate the sensitivity of the shear stress and the Nusselt number.