The outline of the paper is as follows: in Sec. 2, we review accurate and approximate models for polarizability and HOMO-LUMO gap. In Sec. 3, we exhaustively examine the polarizabilities (α) and HOMO-LUMO gaps (∆E HL ) of diverse molecular sets. In doing this, we have extended the QM7-X dataset with functional group information as well as polarizabilities calculated with the hybrid PBE0 functional. In assessing our computational setting, we tested the predictive power of this functional against coupled cluster CCSD(T) calculations, and found an overall accuracy of 1.9%. As a first order approximation to predicting polarizabilities of small organic systems, we consider a linear combination of atomic contributions in Sec. 3.1. In Sec. 3.2, we then perform PBE0 calculations of polarizability (see Sec. 6.1 for computational details) for homologous molecules and explore the relationship with their HOMO-LUMO gaps. A statistical analysis of the (∆E HL , α)-space using a subset of molecules contained in QM7-X dataset is carried out in Sec. 3.3. Our proposed design principle is further discussed and demonstrated on the case of organic photodetectors, see Sec. 4. The computational methods as well as the dataset used are presented in Sec. 6, follow-ing the main conclusions of the manuscript in Sec. 5.