The urinary albumin (UMALB) is the most reliable diagnostic indicator of renal injury in clinical. Attempting to realize the rapid and free reagent measurement of UMALB, the visible-near infrared multiple optical path length spectra of 207 urine samples were collected. By the nonlinear characteristics of multiple optical path length spectra, more information about the component of sample contents can be obtained. The PLS model of the spectra and UMALB was firstly established. Based on it, the PLS-ANN modeling method was built to introduce nonlinear information. By contrast, the PLS-ANN modeling method can obtain a better model to improve the accuracy of quantitative analysis. The R2 of predicted model was 0.951 1 and the RMSEP was 5.02 mg·L-1. The results showed the feasibility of the visible-near infrared multiple optical path length spectroscopy technique for urinary albumin analysis. This research establishes the foundation of detecting the urinary albumin and other components free of reagent conveniently and rapidly.