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For the first time, the potentiality of the sp 2-hybridized group IV-VII radical (R•)-containing molecules to participate in R•-hole interactions was comparatively assessed using •SiF 3, •POF 2 , •SO 2 F, and •ClO 3 models in the trigonal pyramidal geometry. In that spirit, a plethora of quantum mechanical calculations was performed at the MP2/aug-cc-pVTZ level of theory. According to the results, all the investigated R•-containing molecules exhibited potent versatility to engage in R•-hole ... Lewis base interactions with significant negative binding energies for the NCH-based complexes. The strength of R•-hole interactions was perceived to obey the •ClO 3 ... > •SO 2 F ... > •POF 2 ... > •SiF 3 ... Lewis base order, outlining an inverse correlation between the binding energy and the atomic size of the R•-hole donor. Benchmarking of the binding energy at the CCSD/CBS(T) computational level was executed for all the explored interactions and addressed an obvious similarity between the MP2 and CCSD energetic findings. QTAIM analysis critically unveiled the closed-shell nature of the explored R•-hole interactions. SAPT-EDA proclaimed the reciprocal contributions of electrostatic and dispersion forces to the total binding energy. These observations demonstrate in better detail the nature of R•-hole interactions, leading to a convincing amelioration for versatile fields relevant to materials science and drug design. [Display omitted] • The ability of group IV-VII elements to participate in R.•-hole interactions was proved. • R.•-hole interaction strength was inversely correlated with the atomic size of R•-hole donor. • QTAIM analysis unveiled the closed-shell nature of the explored R.•-hole interactions. • SAPT-EDA proclaimed the contributions of electrostatic and dispersion forces. [ABSTRACT FROM AUTHOR]