Microalgae are known as renewable, potential, and sustainable feedstocks for biofuel production. The present work investigated the efficient valorization of green microalgae Chlorella sp. to produce sugars and 5-hydroxymethylfurfural (5-HMF) using thermochemical conversion with a metal-salt (ferric sulfate) as catalyst using a statistical approach and two-step conversion. A statistical approach with a Box–Behnken design was introduced to optimize the conversion for producing sugars. As a result of optimization, 86.46% sugar yield (68.32% glucose yield) was achieved under the condition of 5% biomass and 0.6 g-catalyst/g-biomass at 155 °C and 40 min. Two-step thermochemical conversion was introduced to produce 5-HMF from microalgae. In the first step, sugars were produced from the above optimum condition; in the second step, sugar hydrolysates were converted into 5-HMF by thermochemical conversion without an additional catalyst. In two-step conversion, the maximum 5-HMF yield (37.23%) was achieved at 170 °C and 60 min from the sugar hydrolysate of microalgae obtained from the first-step thermochemical conversion with ferric sulfate. In conclusion, the microalgae as biomass and ferric sulfate as catalyst have availability and the potential to produce biosugars and platform chemicals.