The couple behind mail order business Direct Wines have a £148 million fortune, up £23 million on last year.
Majestic Wine founder John Apthorp was close behind the Laithwaites with a fortune of £125 million.
He owns a £44 million stake in Majestic and also recently made £70 million from selling frozen food retailer Bejam.
Yevgeny Chichvarkin, who owns luxury Mayfair store Hedonism, and John Rudd of Berry Brothers & Rudd both weighed in with fortunes of £120 million.
Producers were also littered across the list, with the Grant Gordon family behind brands like Glenfiddich, Balvenie, Grant’s, Hendrick’s and Sailor Jerry enjoying an estimated worth of £1.9 billion.
The Perrodo family came 14th its family’s Bordeaux portfolio, which includes Margaux estate Château Labégorce Zédé.
Vivian Imerman of Whyte & Mackay was on £355 million, while Tomintoul and Glencadam owners the Hillman family were on £200 million.
Judy Halewood, widow of Halewood International founder John Halewood, has a fortune of £115 million.