Fast-charging capability and calendar life are critical metrics in rechargeable batteries, especially in silicon-based batteries that are susceptible to sluggish Li+desolvation kinetics and HF-induced corrosion. No existing electrolyte simultaneously tackles both these pivotal challenges. Here we report a microscopically heterogeneous covalent organic nanosheet (CON) colloid electrolyte for extremely fast-charging and long-calendar-life Si-based lithium-ion batteries. Theoretical calculations and operando Raman spectroscopy reveal the fundamental mechanism of the multiscale noncovalent interaction, which involves the mesoscopic CON attenuating the microscopic Li+-solvent coordination, thereby expediting the Li+desolvation kinetics. This electrolyte design enables extremely fast-charging capabilities of the full cell, both at 8C (83.1% state of charge) and 10C (81.3% state of charge). Remarkably, the colloid electrolyte demonstrates record-breaking cycling performance at 10C (capacity retention of 92.39% after 400 cycles). Moreover, benefiting from the robust adsorption capability of mesoporous CON towards HF and water, a notable improvement is observed in the calendar life of the full cell. This study highlights the role of microscopically heterogeneous colloid electrolytes in enhancing the fast-charging capability and calendar life of Si-based Li-ion batteries. Our work offers fresh perspectives on electrolyte design with multiscale interactions, providing insightful guidance for the development of alkali-ion/metal batteries operating under harsh environments.