This study addresses the challenge of non-dissociative chemisorption solid-state hydrogen storage by designing heteroatom-doped graphene-supported calcium single-atom materials. Through first-principles calculations, theoretical analysis, and experimental verification, a generalized design principle is established to correlate the inherent properties of dopants with the hydrogen storage capability of carbon-based host materials. An intrinsic descriptor, Φ, is proposed to predict the hydrogen storage properties of single/dual-doped graphene-supported calcium single-atom materials. The dual-doped materials exhibit significantly higher hydrogen storage capabilities compared to single-doped materials, surpassing current best carbon-based hydrogen storage materials. The study highlights the potential of non-dissociative hydrogen storage for clean energy applications, offering a new approach to enhance hydrogen storage capacity and rate.This study addresses the challenge of non-dissociative chemisorption solid-state hydrogen storage by designing heteroatom-doped graphene-supported calcium single-atom materials. Through first-principles calculations, theoretical analysis, and experimental verification, a generalized design principle is established to correlate the inherent properties of dopants with the hydrogen storage capability of carbon-based host materials. An intrinsic descriptor, Φ, is proposed to predict the hydrogen storage properties of single/dual-doped graphene-supported calcium single-atom materials. The dual-doped materials exhibit significantly higher hydrogen storage capabilities compared to single-doped materials, surpassing current best carbon-based hydrogen storage materials. The study highlights the potential of non-dissociative hydrogen storage for clean energy applications, offering a new approach to enhance hydrogen storage capacity and rate.