Solihull is the seventh best place in the country out of 150 education authorities to educate young children, according to the league tables.
The ranking, based on the performance of 11-year-olds in literacy, numeracy and science tests last year, puts the borough's schools ahead of those in the nation's most exclusive addresses such as London's Kensington and Chelsea and Windsor.
But there was bad news for Birmingham, which slipped from last year's 117th position nationally to be ranked 125th despite increasing attainment in maths and science.
Solihull's head of education Coun Ken Meeson (Lab Tipton Green) said the borough's achievement was all the more notable because it was one of the lowest funded authorities in the country.
"We have 5,000 pupils who come into the borough every day to be educated in our schools from neighbouring boroughs," he said.
"They are mainly from Birmingham and Coventry. One of our big beefs with the Government is we are educating these children but we are not getting the same level of grant a school would get if it moved 500 yards across the border."
Schools in urban areas like Birmingham benefit from additional public money to help them cope with the bigger challenges they face.
However, Solihull claims the north of the borough, which includes areas like Chelmsley Wood, is equally deprived.
"One school in the borough told me that if they were just over the border in Birmingham they would pick up an extra £1 million a year in their budget," said Coun Meeson.
"What is remarkable is that Solihull has such high achievement despite being the sixth lowest-paid authority in the country for education.
"That is a constant argument we have with central Government."
The borough saw 84 per cent of primary pupils reaching the required target in English, 80 per cent in maths and 91 per cent in science.
The result saw the authority move 18 places up the table of LEAs from 25 last year.
Meanwhile, Stoke- on-Trent, last year's topperforming authority in the region, fell from 21st to be placed 37th this year.
Despite failing to meet national targets, Birmingham's cabinet member for education Coun Les Lawrence (Con Northfield) praised the city's performance.
"We are proud of the tremendous teaching taking place in all Birmingham primary schools," he said.
Government figures show 74 per cent of Birmingham's 11-year-olds reached the required level four in English in the last academic year, compared with a national average of 79 per cent.
In maths tests, the city's achievement was 70 per cent compared to a national average of 75, and in science it was 83 per cent compared to the national 86 per cent average.
The authority came 11th out of the region's 14 LEAs, compared to last year's ninth place. Sandwell maintained its bottom position regionally for primary performance and was ranked joint 144th nationally alongside Bristol.
Coun Ian Jones, Sandwell's cabinet member for schools, said: "The challenge now is to maintain our progress and climb up from our position at 144th equal."