Herein, we developed and designed a novel ratiometric optical chemisensor film for determining Al(III) and Cu(II) in low concentration ranges. The chemisensor film consists of (a) antibacterial drug Ciprofloxacin (CPFX) [1-cyclopropyl-6-fluoro1,4-dihydro-4-oxo-7-(piperaziny-l-yl) quinolone-3carboxylic acid] and (b) a reference dye 5,10,15,20- tetrakis (pentafluorophenyl) porphyrin (TFPP) in a polyvinyl chloride (PVC) matrix. PVC was applied as a homogeneous system for mixing CPFX and TFPP. The emission intensity of the CPFX in the PVC matrix varies depending on the concentrations of the Al(III) and Cu(II) ions. When the sensor film is immersed in different Al(III) concentrations, a significant fluorescence enhancement of the CPFX at (427 nm) is observed. Furthermore, the fluorescence intensity of the red emission of the TFPP dye at (644 nm) does not alter. However, in the presence of Cu(II) ions, a considerable emission quenching of the CPFX peak at (427 nm) is observed. PVC provides a great permeability and penetration facilities of dissolved ions that make the sensor film sensitive to Al(III) or Cu(II) changes outside the matrix. The film displays immense sensitivity depending on their distinctive optical characteristics of CPFX and detection capabilities within a low detection limit LOD for Al(III) and Cu(II). The LOD values were estimated to be 2.05 x 10−7 M and 1.04 x 10−7 M respectively with a relative standard deviation RSDr (1%, n=3). Density functional theory (DFT) and the time-dependent DFT (TDDFT) theoretical calculations were performed to study Cu(II) and Al(III) complexation structures and their electronic properties in solution and in the sensor film. The interference of the chemisensor film was examined using different cations and the chemisensor provides significant selectivity. We develop a new ratiometric chemisensor based on PVC polymer film for Al(III) and Cu(II) detection.