Instructive materials able to drive cells, in particular the differentiation of stem cells toward osteoblastic lineages have been investigated as a promising strategy for bone tissue engineering. Inorganic ions, such as phosphorous, calcium, silicon and strontium, have been used in bone regeneration strategies as instructive ions for material based approaches. The use of effective inorganic ions are being investigated as a promising approach for bone regeneration applications mainly due to the fact that are highly available and cost-effective and thus, reducing the need of using expensive and less stable growth factors. The aim of present study is to investigate the effect of the release of silicon (Si) and calcium (Ca) ions from blend of starch and poly-caprolactone (SPCL) scaffolds on the osteogenic behavior of human adipose stem cells (hASC). The scaffolds were developed by a wet-spinning technique and two different solutions were used as coagulation bath, one containing Ca and Si ions and other one containing only Si ions. The composition of the scaffolds as well as their mechanical properties was also evaluated. Our study showed that both scaffolds were able to sustain cell attachment and induce their differentiation into the osteogenic lineage in basal medium, i.e., in the absence of osteogenic factors. The scaffolds containing both ions, Si and Ca, had a stronger influence on the osteogenic differentiation of hACS than the scaffolds containing only Si ion. Thus, present work highlight the importance of combining Si and Ca ions in the control of cellular response, namely, cell differentiation and/or in stem cells recruitment upon implantation of a cell-free scaffold, and thus, avoiding the use of costly growth factors.