Photochemical crystal-to-liquid transition generally needs UV light as a stimulus and it is even more challenging to carry out below 0 oC. Here, we design a series of 4-alkylthioarylazopyrazoles as molecular solar thermal batteries, which show bidirectional visible-light-triggered photochemical trans-crystal ↔ cis-liquid transitions below ice point (-1 oC). Through co-harvesting visible-light energy and low-temperature ambient heat, high energy density (0.25 MJ kg-1) is achieved. Further, the rechargeable solar thermal batteries devices are fabricated, which can be charged by blue light (400 nm) at -1 oC. Then, the charged devices can release energy on demand in the form of high-temperature heat. Under green light (532 nm) irradiation, the temperature difference between the charged devices and the ice-cold surrounding is up to 13.5 oC. This study paves the way for the design of advanced molecular solar thermal batteries that store both natural sunlight and ambient heat over a wide temperature range.