As a novel performance, to attempt cinnamic acid derivatives (CAs), including caffeic acid, ferulic acid, and p‐coumaric acid quantification by fluorescence spectroscopy in complex chemical systems with unknown interferences in water, creating second‐order data was demanded. In the present study, α,β‐cyclodextrin (α,β‐CD) inclusion complexes application for second‐order data generation joined with bilinear least squares/residual bilinearization (BLLS/RBL) and parallel factor analysis (PARAFAC) as second‐order calibration methods. In the first step, inclusion complexes formation between CA analytes with α,β‐CDs at the optimized condition was evaluated. The resolution of model compounds was possible in the base to the differences in the fluorescence spectral changes of the inclusion complexes signals of the investigated analytes as a function of CD concentrations opening a new approach for second‐order data generation. In light of these facts, due to severe profiles overlapping between CAs, we propose creating third‐order data for each sample using α and β‐CD media to produce inclusion complexes as a new additional selectivity mode while the obtained data in two media were augmented next. Three‐way arrays were constructed by stacking augmented data in a third way and then analyzed by two powerful second‐order calibration methods (BLLS/RBL and PARAFAC) to get spectral and concentration profiles of CAs as a function of α,β‐CD concentrations. The concentrations were between 0 to 6.0, 0 to 10.0, and 0 to 8.0 mg L−1 for caffeic acid, ferulic acid, and p‐coumaric acid, respectively. The results of both methods are in good agreement, and reasonable recoveries are achieved.