Puyfontaine joined Le Figaro in order to develop relations between the newspaper and the Grandes écoles. He worked there for 3 years while completing his education. After a short period as a consultant at Arthur Andersen, he went to Indonesia to perform his national service. He then joined back Le Figaro and managed La Solitaire du Figaro under the direction of Philippe Villin. In 1995 he joined Emap. He began by managing Télé Poche and Studio Magazine and was in charge of the purchase of Télé Star and Télé Star Jeux. He created the Emap Star division where he became Deputy director, and in July 1998 he was appointed Managing Director of Emap France group. The creation of the Emap Star division, which quickly became a heavyweight of the TV press, paved the way for his appointment as Chief Executive Officer of the group. He was also a member of the board of Emap, Emap Digital Worldwide and trustee of Emap Metro in the UK. At the same time, he became trustee and President of Audipresse, the Association for the promotion of magazine publishers. Arnaud de Puyfontaine was also member of the board of the general information press and magazines' Union. In 2006 Emap plc sold its French subsidiary, which joined Mondadori group. Thanks to this purchase, the French magazine sector was opened for the Italian media group. In April 2006 Arnaud de Puyfontaine became President of Mondadori France holding, which aims at developing new activities. In this regard, he was appointed Managing Director for digital business of the Mondadori group. He resigned in August 2008 and became senior advisor to Maurizio Costa, vice-president and trustee of Arnoldo Mondadori Editore group. In October 2008 Nicolas Sarkozy launched national consultations on printed media and nominated Arnaud de Puyfontaine as President of the "Print, transport, distribute, finance : how to regenerate industrial process of printed media?" working group. Later, he was tasked by the President of the French republic with a mission to follow up and implement decisions that have been taken and have influenced recent evolvements of the sector. In April 2009 he created Elteg with Christophe Agnus and Rémi Poulet. Elteg is a technology and innovation company involved in Enterprise Content Management with its division named Walabiz, hotel industry, and publishes Sopixi, an e-shopping and free website development platform. On 15 May 2009 he became CEO of The National Magazine Company, British subsidiary of Hearst Corporation, responsible for European activities. In June 2011, following the acquisition of publications sold by Lagardère group, he was appointed Executive Vice-President of Hearst Magazine International. In May 2012 De Puyfontaine joined the board of Schibsted, one of the leading media groups in Scandinavia. In January 2014 de Puyfontaine joined Vivendi as Senior Executive Vice President for media and content activities. On 24 June 2014 he was elected Chairman of the Management Board.
His maternal grandfather, André-Marie Gerard, was editor-in-chief of L'Aurore from 1957 to 1960. Later, he was director of TV news programmes at the RTF and subsequently became Inspector-General of the ORTF.