Spin, the intrinsic angular momentum of an electron, is increasingly being recognized as a versatile tool in the development of next-generation technologies, including quantum computing, sensing, and communication, which exploit quantum phenomena. The burgeoning theoretical understanding coupled with technological advancements have catalyzed research efforts aimed at controlling and manipulating the optical, electrical, magnetic, and thermal properties of materials through the modulation of spin states. Among the myriad of techniques available for investigating these spin-dependent properties, Electron Spin Resonance (ESR), sometimes referred to as electron paramagnetic resonance, stands out as one of the most direct and potent methods to probe electron spin dynamics irrespective of the material environment. ESR furnishes insightful data on the states of individual spins and clusters, spin coherence via relaxation time measurements, and inter-spin distances from spin–spin interaction measurements. Additionally, ESR facilitates the manipulation of spin systems by tailoring the Zeeman energy through the modulation of the external magnetic field, and critically, by the remote manipulation of spins via the application of microwave pulses at resonance frequencies. Modern ESR experimental setups are versatile and can be employed across a wide temperature spectrum—from a few Kelvin, where quantum effects are pronounced, to room temperature and beyond. This adaptability enhances the utility of ESR in investigating the spin-dependent properties in condensed matter systems. Notwithstanding the tremendous potential and advantages that ESR offers, it remains underutilized, especially when compared to inelastic neutron scattering (INS) and nuclear magnetic resonance, despite the latter being more expensive and INS being less accessible. In this review, we elucidate the fundamental principles of ESR, with an emphasis on magnetic and spin interactions in solids, and explore the potential of ESR in advancing the understanding of spin properties across a diverse array of materials science disciplines. We commence with a concise introduction to spin-related physics, followed by the application of ESR in characterizing spin systems. As such, this review aims to serve as a valuable resource for a broad audience, ranging from novices to experts, who are keen on unraveling spin phenomena and dynamics in materials science and condensed matter physics.