VO(acac)2 and the in situ generated VO(Salen) complex were immobilized on the covalently modified graphene oxide (GO) with ethylenediamine (en) and designated as VO(acac)2@en‐GO and VO@Salen@en‐GO, respectively. Characterization of the prepared compounds was carried out with FT‐IR, XRD, ICP, CHN, Raman, SEM, TEM, and BET techniques. The SEM results confirmed the formation a nanofiber network and nanointerconnected needles. The prepared immobilized complexes were then used as heterogeneous catalysts for epoxidation of some allyl alcohols such as geraniol, trans‐2‐hexene‐1‐ol, and 1‐octen‐3‐ol. Based on the results obtained by GC and GC–mass analyses, epoxidation of geraniol with 97% conversion and 100% selectivity seemed promising. Readily recycling of the catalyst and reusing for four successive catalytic runs without significant loss of activity revealed that this catalysis system deserves nomination for practical application.