In Spain...on the road Again which also features American food writer Mark Bittman and actress Claudia Bassols, he travels around the country and interviews some of its top chefs including Ferran Adria and Juan Mari Arzak.
Batali, who has lived in Spain and has known Paltrow for a decade, said the Oscar-winning actress was fun to travel with.
"She's got a great perspective on the world and doesn't need or care to be famous when you are with her," the 47-year-old chef said.
He spoke about the differences in Italian and Spanish cuisine and what makes the food so distinctive.
Q: What was the idea behind the show?
A: "The show idea is to travel around Spain and view it both from a professional gastronomic point of view such as mine or Mark's, and from a less professional but equally interested (view) such as Claudia's and Gwyneth's, to see what it is that is going on in Spain that has me so excited. And in fact we do. We see all kinds of crazy simple things from housewives and home-cooked (meals) to molecular gastronomy in the hands of nitrogen experts."
Q: How would you compare and contrast Spanish and Italian cuisines?
A: "The flavours and technical components of Mediterranean cooking whether it's Northern African or Southern European are all very similar, and it's interesting to see what unifies the entire nation's cuisines as it does in Italy – it's the use of olive oil. In Spain also it's olive oil. What's lacking in Italy from a Spanish perspective is the way they do their rice, and what's lacking in Spain from the Italian perspective is the fact that they don't do pasta, other than little angel hairs."
Q: What is your favourite Spanish dish or food?
A: "I would say one of my favourite places that we were at is a place named Galicia in the far north-western part of the country. Having simple shell-fish or seafood, steamed or cooked with just a squeeze of lemon, and have it taste like it's really from that specific geography is what makes me very excited."
Q:What is the one thing that you can't cook without in your kitchen?
A: "Extra virgin olive oil, no question. It is the single-most used product in my house and my kitchen."
Q: What do you cook for yourself?
A: "If I cook at home alone, I'll make some toast with cheese on it. I cooked for my family yesterday and I made osso bucco with sweet corn. I love to cook at home."