To provide a polyol ester having high compatibility to fluorocarbon substitutes, good low-temperature fluidity and excellent electrical insulation and provide its production process.

This polyol ester is a mixture of 1,1,1,2-tetrafluoroethane and a polyol ester at a weight ratio of 9/1 and has a low temperature-side separation temperature of ≤-70°C, a flow point of ≤-35°C and a volume resistivity of ≥1.0×1015. It can be produced by preparing an acid fluoride from carbon monoxide and a 4-12C monoolefin wherein at least one of the carbon atoms forming the double bond is tertiary carbon atom, reacting the acid fluoride with neopentyl glycol and removing ≥1wt.% of the high-boiling component of the obtained polyol ester by distillation.