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Rhodamine B (RhB) films prepared via spin coater on polyacetate flexible substrates. The X-ray diffraction spectroscopy has been done for RhB/polyacetate flexible substrate and displays an amorphous structure of RhB films in the various thicknesses in the range of 74–303 nm. K-K relations used for determining the refractive index and exhibits a normal dispersion at λ > 600 nm and an anomalous dispersion at λ < 600 nm. The electronic transitions reveal two bands of absorbance Q band which due to the first π→π* transitions and Soret band due to the second π → π * transitions. Also, other linear optical constant such as absorption coefficient, band energy gap, dielectric constants, and optical conductivity were discussed. On the other hand, the first (χ (1) ) and third (χ (3) ) orders of nonlinear optical susceptibilities as well as a nonlinear refractive index (n 2) were calculated and discussed. The electrical and optical conductivities demonstrated the high absorption of RhB/flexible substrates inferring the chance of utilizing these films as optoelectronic gadgets. • Flexible optoelectronic materials have an increasing interest in the advancement of solar energy and biomedicine. • Investigated the optical spectroscopy by Kramers-Kronig (K‑K) method For Rhodamine B (RhB) films. • Calculated the nonlinear optical constants (χ(1)), (χ(3)) and nonlinear refractive index (n 2). • Calculated the electrical and optical conductivities. [ABSTRACT FROM AUTHOR]