This study focuses on the development of new biocompatible and biodegradable particle gel scaffolds based on PCL-HBPG/1SiHBPG triblock copolymers composed of a polycaprolactone (PCL) core and two outer blocks of trimethoxysilyl end-capped hyperbranched polyglycidol (HBPG/1SiHBPG) that have the potential to be used in soft tissue regeneration. The relationship between the gel’s composition, structure, mechanical properties, and performance has been investigated for the first time and the copolymer design parameters have been optimized. The particle gel scaffolds were formed from the concentrated dispersions of the most hydrophobic PCL-45HBPG/1SiHBPG at low temperatures, and were the result of the numerous hydrogen bonds formed from the HBPG/1SiHBPG moieties as well as the formation of siloxane crosslinks (i.e., Si–O–Si bonds). These gels were formed in the physiological temperature range. Gels with a mechanical strength that gradually increases were formed from the physically crosslinked PCL-45HBPG/1SiHBPG particles effectively and safely, in the absence of UV radiation. They feature high elasticity and undergo enzyme-triggered disassembly. The gels are biocompatible and have the potential to invoke cell attachment and differentiation in the absence of exogenous biological stimuli. A successful outcome of this study will be the prospect of a new approach for tissue regeneration that is currently not available.