A better application of Soundless Chemical Demolition Agents (SCDAs) in fragmentation is based on our knowledge on their expansive characteristics. In this study, an integration of experimental and modeling approaches was developed to investigate SCDA expansion and corresponding cracking processes of Steel Fiber Reinforced Concrete (SFRC). The expansive properties of the selected SCDA were first estimated by free volume expansion (FVE) tests and expansion pressure (EP) tests. Then, cracking experiments were performed on 150 mm cubic SFRC blocks with a predrilled hole, and the cracking process was monitored by using Acoustic Emission (AE) and Digital Image Correlation (DIC) techniques. Generally, the cracking process can be divided into three phases, termed micro-cracking phase, macro-cracking phase, and failure phase. It was observed the hole diameter and fiber content exert significant influences on the cracking process. The crack initiation time was shortened as the hole diameter increases, while it was prolonged with increasing fiber content. The cracked area ratio was further proposed and measured to assess the cracking performance of SCDA. The ratio increases from 2.73% to 8.293% as the hole diameter increases from 16 mm to 26 mm, while it decays from 9.75% to 1.823% as the fiber content increases from 0 to 2.4%. After verified with the experimental data, a modified Concrete Damaged Plasticity (CDP) model was adopted to extend the fragmentation of SFRC from the centimeter scale to the meter scale. The simulations were conducted on SFRC models with various hole diameters, spacings, and fiber contents. The simulated results show the fragmentation performance is related to both hole parameters (e.g., hole diameter, spacing, etc.) and SFRC properties (including elastic modulus, fiber content, etc.). In particular, the cracked area (DamageT > 0.9) varies directly with hole spacing, diameter, and fiber content. Built on the simulated results, an empirical equation was formulated to quantitatively evaluate the fragmentation ability of individual holes. In addition, extra simulations were conducted to assess the efficiency of SCDA in cracking PC/SFRC beams of various sizes. The obtained cracked area tends to decrease first and then approach a constant value with increasing beam sizes, indicating the existence of a size effect, which is primarily due to variations in concrete restraints provided by beams of different sizes. This work quantitatively evaluates expansive properties of SCDA and SCDA-induced cracks, and thus provides a reference for optimizing the field application parameters.