The invention discloses a production system and a production technology for 99-grade pentaerythritol. The production system comprises a feeding unit, a reaction unit, an aldehyde removal unit, an alcohol removal unit, an evaporation unit, a crystallization unit, a centrifugal unit and a drying unit. A sodium method is adopted to continuously produce the pentaerythritol, formaldehyde and acetaldehyde are taken as raw materials to carry out condensation reaction under caustic soda liquid catalysis, formic acid is used for neutralization after reaction ends, and therefore, pentaerythritol and a byproduct, i.e., sodium formate are generated; then, through working procedures, including aldehyde removal, alcohol removal, evaporation, crystallization, separation, drying and the like, the 99-gradepentaerythritol finished product is obtained. According to the production system and the production technology, a pentaerythritol, dipentaerythritol and tripentaerythritol co-production technology can be realized, the generation of byproducts can be reduced so as to improve purity and yield, the removal rate of methyl aldehyde can be 99.9% by aldehyde removal, and the quantity of residual methylaldehyde in the product is reduced. The production system has the advantages of high automation degree and small labor intensity and personnel intensity, meanwhile, the production efficiency of the pentaerythritol is improved, and the production cost is reduced.