The effect of aluminum (Al) concentration on the surface plasmon resonance (SPR) band position of aluminum/polyvinylpyrrolidone (Al/PVP) composite nanofibers was investigated to strengthen nonlinear absorption (NLA) and widen its spectral range. With increasing Al content in PVP nanofibers, the SPR band was shifted towards excitation wavelength and an improved NLA response was achieved. The NLA response was examined both experimentally, by conducting Z-scan experiments, and theoretically, using two models. In the first model, the contributions of one-photon absorption (OPA), two-photon absorption (TPA), excited state absorption (ESA) and saturated absorption (SA) are considered. The second model, on the other hand, is a model that is widely used in the literature, and while taking into account the contributions of OPA and TPA, it neglects the ESA. The first model provides more accurate results due to the high concentration of free carriers in the samples examined. In order to reveal the contribution of Al to the nonlinear absorption, a laser excitation wavelength of 532 nm was chosen to minimize both the defect-assisted sequential and genuine two-photon absorption contributions of PVP. While the nonlinear absorption of pure PVP is quite weak, the NLA performance of Al/PVP nanofibers significantly improved as the Al content increased. As the amount of Al increased, the aggregation effect increased and a broadening and red shift in the SPR band were observed in the plasmonic behavior. This indicates a decreasing interparticle distance in Al particles. The sample with the highest amount of Al is anticipated as a potential candidate for optical limiting (OL) applications due to its superior NLA performance and SPR band furthest towards the near infrared (NIR) region, allowing a wider range of wavelength set to be used in OL applications.