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Maria Papaioannou began their work experience as a Customer Service Employee at the Hellenic Telecommunications Organisation in 2010. In 2012, they worked as a Telecommunications Research Intern at WirelessLAN. Maria then transitioned to the University of Southampton in 2014 as an Outreach and Public Engagement Assistant, where they designed science demonstrations and engaged with students, families, and teachers. Maria later became a Module Demonstrator at the University of Southampton in 2015. In 2018, they joined ALL.SPACE as the Lens Antenna Engineering Lead before moving on to become the Director of Lens Antenna Engineering in 2019.

Maria Papaioannou completed their Unified Lyceum Certificate at the 3rd Unified Lyceum of Drama, Greece, from 2003 to 2006. Maria then pursued a Diploma in Electrical and Computer Engineering with a specialization in Telecommunications at Aristotle University of Thessaloniki (AUTH) from 2006 to 2013. Later, they obtained their Doctor of Philosophy (Ph.D.) in Nanophotonics and Metamaterials from the University of Southampton from 2013 to 2017. In 2020, they also obtained a certification in "Skills for Inclusive Conversations" from LinkedIn.