Conductive hydrogels are promising material candidates in fields ranging from flexible sensors and electronic skin applications to personalized medical monitoring. However, developing intrinsically conductive polymer hydrogels (ICPHs) with high mechanical properties and excellent printability is still challenging. Here, we introduce a simultaneous polymerization acceleration and mechanical enhancement (SPAME) strategy to construct PEDOT-based ICPHs via the rational design of coordinative and orthogonal ruthenium photochemistry (CORP). This orthogonal photochemistry triggers the oxidative polymerization of EDOT and the coupling of phenols within seconds under blue light irradiation. Benefiting from the bifunctional EDTA-Fe design, the photoreleased Fe(III) accelerated the EDOT polymerization and shortened the preparation time of ICPHs to a few seconds. At the same time, the addition of EDTA-Fe enhanced their mechanical properties, and both the critical strains and maximum stresses of the hydrogel doubled. Furthermore, the introduction of phenol residues in PAA-Ph significantly shortened the gelation time from several minutes to about 7 s. Thus, this fast and controllable CORP chemistry is compatible with standard printing techniques for engineering hydrogels for complex multifunctional structures for multifunctional bioelectronics and devices.